RU2411255C2 - Polyurethanes, articles and coatings made from said polyurethanes, and production methods thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a partial continuation of the patent application of the United States, reg. No. 10/932641, filed September 1, 2004, and United States Patent Applications Reg. No. 11/303670, 11/303422, 11/303892, 11/303671 and 11/303832, which were sent for consideration on December 16, 2005. Each of the above applications is incorporated here by reference.

BACKGROUND

I TECHNICAL FIELD

The present invention relates to polyurethanes and poly (urethane ureas) obtained from branched polyols, branched polyisocyanates and / or trimers of polyisocyanates, to products and coatings made from them, as well as to methods for their production.

II TECHNICAL SUGGESTIONS

A number of organic polymeric materials, such as plastics, such as polycarbonates and acrylic polymers, have been developed as alternatives and substitutes for glass for applications such as optical lenses, fiber optics, windows and automobiles, marine and aviation transparent products. For example, in aircraft glazing, both polycarbonates such as LEXAN ^® and acrylic polymers are widely recognized. Such polymeric materials can provide advantages relative to glass, including resistance to breakage or resistance to penetration, less weight for a given application, flexibility, easy formability and tintability. Unfortunately, there are some serious drawbacks associated with both polycarbonates and acrylic polymers. Polycarbonates are easily scratched, and if they are exposed to direct sunlight and a harmful environment, it soon becomes difficult to look through them. Acrylic polymers, although not as prone to scratching as polycarbonates, do not have the physical properties of polycarbonates, such as the deformation temperature due to thermal heating and resistance to shock loads. Some “high impact” polycarbonates may have inconsistent toughness, which may deteriorate over time, low crack propagation resistance (K-factor, K-factor), low optical characteristics, low solvent and low resistance to weathering. Even if polycarbonates can show good impact resistance when impacting at low speeds, at high impact speeds, above approximately 1,100 ft / s (335.3 m / s), such as those shown in ballistics, a 9 mm bullet (125 grains) fired from approximately 20 feet (6.1 m) at a speed of approximately 1350 ft / s (411 m / s), it can easily pass through 1 inch (2.5 cm) polycarbonate plastic.

In addition, as a rule, polycarbonates are extruded, which can give optical distortions in the extrudate in the direction of extrusion. For optical applications such as fighter cockpit lights, polycarbonates typically have to undergo an additional process step to remove distortion, which increases costs. In addition, some polycarbonates are birefringent, which can also cause optical distortion. For example, the Abbe LEXAN number is 34. A higher Abbe number indicates a better visual sharpness of the image and less chromatic aberration.

Therefore, in the art there is a need to develop polymers that can be used to manufacture products having good optical properties, high impact resistance, high impact strength, high K coefficient, good ballistic resistance, good solvent resistance and good resistance to atmospheric influences. Also desirable is the ability to manufacture articles by injection molding or reaction injection molding rather than extrusion.

SUMMARY OF THE INVENTION

A discussion of various aspects and embodiments of the polyurethanes and poly (urethane ureas) of the present invention is grouped below. Although various aspects of the invention are grouped for discussion purposes, such grouping is not intended to limit the scope of the present invention, and aspects of one of the groups may relate to the subject of the invention of other groups.

Group A

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.05 to about 0.9 equivalents of at least one branched polyol containing from 4 to 12 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.1 to about 0.95 equivalents of at least one diol containing from 2 to 18 carbon atoms;

where said components are substantially free of polyester polyol and polyether polyol, and where the reaction components are held at a temperature of at least about 100 ° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) approximately 1 equivalent of 4,4'-methylene-bis- (cyclohexyl isocyanate);

(b) from about 0.3 to about 0.5 equivalent of trimethylolpropane; and

(c) from about 0.3 to about 0.7 equivalents of 1,10-dodecanediol, butanediol or pentanediol;

where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides a product consisting of polyurethane containing the reaction product of components including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 12 carbon atoms;

where the components are substantially free of polyester polyol and polyether polyol, and where the product has a Gardner impact resistance of at least about 200 inch · lb (23 J) in accordance with ASTM-D 5420-04.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, including the stage of simultaneous interaction of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 12 carbon atoms;

where the components are substantially free of polyester polyol and polyether polyol, and where the reaction components are held at a temperature of at least about 100 ° C. for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and

(b) reacting a polyurethane prepolymer with at least one diol containing from 2 to 12 carbon atoms to form a polyurethane,

wherein said reaction components are held at a temperature of at least about 100 ° C. for at least about 10 minutes.

Group B

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) an urethane prepolymer with isocyanate functionality containing the reaction product of components including:

(i) about 1 equivalent of at least one polyisocyanate and

(ii) from about 0.1 to about 0.5 equivalent of at least one diol containing from 2 to 18 carbon atoms, and

(b) from about 0.05 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) up to about 0.45 equivalent of at least one diol containing from 2 to 18 carbon atoms,

wherein said components are substantially free of polyester polyol and polyether polyol.

Group C

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate has at least three isocyanate functional groups; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups;

wherein said components are substantially free of polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate);

(b) about 1.1 equivalents of butanediol; and

(c) about 0.1 equivalent of an isophorondiisocyanate trimer.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, including the stage of simultaneous interaction of components, including:

(a) at least one trimer of a polyisocyanate or a branched polyisocyanate, wherein the polyisocyanate has at least three isocyanate functional groups; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups;

where the components are essentially free of polyester polyol and polyether polyol.

Group D

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or combinations thereof.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate);

(b) from about 0.3 to about 0.5 equivalent of trimethylolpropane;

(c) from about 0.2 to about 0.5 equivalent of bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) sulfone;

(d) from about 0.2 to about 0.5 equivalent of 1,4-cyclohexanedimethanol and

(e) from about 0.2 to about 0.5 equivalent of 3,6-dithia-1,2-octanediol.

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate has at least three isocyanate functional groups;

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups; and

(c) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or combinations thereof.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, comprising the step of simultaneously reacting components, including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or combinations thereof.

In other non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and

(b) reacting the polyurethane prepolymer with at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or a combination thereof, to form a polyurethane.

Group E

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol;

where these components are essentially free of simple polyether polyol and an amine curing agent, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate);

(b) about 0.3 equivalent of trimethylolpropane;

(c) from about 0.5 to about 0.55 equivalents of butanediol or pentanediol, and

(d) from about 0.15 to about 0.2 equivalents of polyhexylene carbonate diol;

where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, comprising the step of simultaneously reacting components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol;

where these components are essentially free of simple polyether polyol and an amine curing agent, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and

(b) reacting the polyurethane prepolymer with at least one polycarbonate diol to form a polyurethane.

Group F

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol and

(d) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms;

where these components are essentially free of polyether polyol and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, comprising the step of simultaneously reacting components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol and

(d) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms;

where these components are essentially free of polyether polyol, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and

(b) reacting the polyurethane prepolymer with at least one polycarbonate diol and with at least one diol containing from 2 to 18 carbon atoms to form a polyurethane;

where these components are essentially free of polyether polyol.

Group G

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) from about 0.01 to about 0.3 equivalents of at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol, and mixtures thereof; and

(d) from about 0.1 to about 0.7 equivalents of at least one aliphatic diol;

where these components are essentially free of simple polyether polyol and an amine curing agent, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate);

(b) about 0.3 equivalent of trimethylolpropane;

(c) from about 0.5 equivalent of decanediol and

(d) approximately 0.2 equivalent of polycaprolactone polyol;

where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing polyurethane, including the stage of simultaneous interaction of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) from about 0.01 to about 0.3 equivalents of at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol, and mixtures thereof; and

(d) from about 0.1 to about 0.7 equivalents of at least one aliphatic diol;

where these components are essentially free of polyether polyol and an amine curing agent.

In other non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and

(b) reacting the polyurethane prepolymer with at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol, and mixtures thereof, and from about 0.1 to about 0.7 equivalents of at least one aliphatic diol c the formation of polyurethane.

Group H

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) a prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol;

(3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof; and

(b) at least one diol containing from 2 to 18 carbon atoms.

In other non-limiting embodiments, the present invention provides polyurethanes containing a reaction product of components, including:

(a) a prepolymer, which is a reaction product of components including:

(1) an aliphatic or cycloaliphatic diisocyanate;

(2) polycaprolactone diol;

(3) polyethylene glycol and

(4) a copolymer of polyoxyethylene and polyoxypropylene; and

(b) at least one diol containing from 2 to 18 carbon atoms.

In some non-limiting embodiments, the present invention provides methods for producing polyurethane, which include the steps of:

(a) interactions of components, including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof;

with the formation of a polyurethane prepolymer and

(b) reacting the prepolymer with at least one diol containing from 2 to 18 carbon atoms to form a polyurethane.

Group I

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) at least one urea prepolymer with isocyanate functionality containing the reaction product:

(1) at least one polyisocyanate and

(2) water; and

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where these components are essentially free of amine curing agent.

In some non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which include the steps of:

(a) the interaction of at least one polyisocyanate and water with the formation of a urea prepolymer with isocyanate functionality and

(b) reacting a reaction product of components containing a urea prepolymer with isocyanate functionality with at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where these components are essentially free of amine curing agent.

Group J

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) at least one urea prepolymer with isocyanate functionality containing the reaction product:

(1) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and

(2) water; and

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups.

In some non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which include the steps of:

(a) the interaction of at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates and water to form a urea prepolymer with isocyanate functionality and

(b) reacting a reaction product of components containing a urea prepolymer with isocyanate functionality with at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where these components are essentially free of amine curing agent.

Group K

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) at least one urethane-urea prepolymer with isocyanate functionality containing the reaction product:

(1) at least one isocyanate functional urethane prepolymer containing the reaction product:

(i) a first amount of at least one polyisocyanate and

(ii) a first amount of at least one branched polyol; and

(2) water;

with the formation of a urethane urea prepolymer with isocyanate functionality and

(b) a second amount of at least one polyisocyanate and a second amount of at least one branched polyol.

In some non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which include the steps of:

(a) the interaction of at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of an urethane prepolymer with isocyanate functionality;

(b) reacting an urethane prepolymer with isocyanate functionality with water and a polyisocyanate to form a urethane urea prepolymer with isocyanate functionality and

(c) reacting the reaction product of components containing a urethane urea prepolymer with isocyanate functionality with at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where these components are essentially free of amine curing agent.

Group L

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) at least one urethane-urea prepolymer with isocyanate functionality containing the reaction product:

(1) at least one isocyanate functional urethane prepolymer containing the reaction product:

(i) a first amount of at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanates contain at least three isocyanate functional groups; and

(ii) a first amount of at least one aliphatic polyol; and

(2) water;

with the formation of a urethane urea prepolymer with isocyanate functionality and

(b) a second amount of at least one polyisocyanate and a second amount of at least one aliphatic polyol.

In some non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which include the steps of:

(a) the interaction of at least one polyisocyanate selected from the group comprising trimers of a polyisocyanate and branched polyisocyanates, and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, with the formation of an urethane prepolymer with isocyanate functionality;

(b) reacting an urethane prepolymer with isocyanate functionality with water and a polyisocyanate to form a urethane urea prepolymer with isocyanate functionality and

(c) reacting the reaction product of components containing a urethane urea prepolymer with isocyanate functionality with at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

where these components are essentially free of amine curing agent.

Group M

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) from about 0.1 to about 0.9 equivalents of at least one aliphatic diol containing from 2 to 18 carbon atoms; and

(d) at least one amine curing agent,

wherein said components are substantially free of polyester polyol and polyether polyol.

In other non-limiting embodiments, the implementation of the present invention provides methods for producing poly (urethane urea), which include the stage of simultaneous interaction of components, including:

(a) at least one polyisocyanate;

(b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) at least one aliphatic diol containing from 2 to 18 carbon atoms; and

(d) an amine curing agent,

wherein said components are substantially free of polyester polyol and polyether polyol.

Group N

In some non-limiting embodiments, the present invention provides poly (urethane ureas) containing a reaction product of components including:

(a) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups;

(b) from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups;

(c) at least one amine curing agent;

wherein said components are substantially free of polyester polyol and polyether polyol.

In some non-limiting embodiments, the implementation of the present invention provides methods for producing poly (urethane urea), which include the stage of simultaneous interaction of components, including:

(a) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates;

(b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

(c) at least one aliphatic diol containing from 2 to 18 carbon atoms; and

(d) an amine curing agent,

wherein said components are substantially free of polyester polyol and polyether polyol.

Group O

In some non-limiting embodiments, the present invention provides polyurethane materials comprising a first part of crystalline particles that are self-oriented and bonded together to fix their orientation along the first crystallographic direction, and a second part of crystalline particles that are self-oriented and bonded together to fix their orientation along the second crystallographic direction moreover, the first crystallographic direction differs from the second crystallographic direction, where these crystalline particles comprise at least about 30% of the total volume of the polyurethane material.

Group P

In some non-limiting embodiments, the present invention provides methods for producing a polyurethane powder coating composition, which comprise the steps of: reacting at least one polyisocyanate with at least one aliphatic polyol to form, as a rule, a solid prepolymer with hydroxyl functionality; melting a prepolymer with hydroxyl functionality; melting at least one, typically solid polyisocyanate to form a molten polyisocyanate; mixing the prepolymer with hydroxyl functionality and the molten polyisocyanate to form a mixture and curing the mixture to form, as a rule, a solid powder coating composition.

In other non-limiting embodiments, the present invention provides methods for producing a polyurethane powder coating composition, which comprise the steps of: reacting at least one polyisocyanate with at least one aliphatic polyol to form, as a rule, a solid prepolymer with hydroxyl functionality; dissolving the prepolymer with hydroxyl functionality in a first solvent to form a first solution; dissolving at least one, usually solid polyisocyanate in a second solvent, which is the same solvent or compatible with the first solvent, to form a second solution; mixing the first and second solutions and removing substantially all of the solvent to form, as a rule, a solid powder coating composition.

Group Q

In some non-limiting embodiments, the implementation of the present invention provides polyurethane compositions containing at least one polyurethane containing the reaction product of components including:

(a) (i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and combinations thereof.

In other non-limiting embodiments, the present invention provides polyurethane compositions comprising:

(a) at least one polyurethane containing a reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or a combination thereof; and

(b) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and mixtures thereof.

In other non-limiting embodiments, the present invention provides polyurethane compositions comprising:

(a) a polyurethane containing a reaction product of components including:

(i) a prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof; and

(ii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and mixtures thereof.

In other non-limiting embodiments, the present invention provides polyurethane compositions comprising:

(a) at least one polyurethane containing a reaction product of components including:

(i) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate or branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and

(ii) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

(b) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and mixtures thereof.

In other non-limiting embodiments, the present invention provides a poly (urethane urea) composition comprising:

(a) at least one poly (urethane urea) containing a reaction product of components including:

(i) at least one prepolymer with isocyanate functionality containing the reaction product:

1. At least one polyisocyanate and

2. Water; and

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where these components are essentially free of amine curing agent; and

(b) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and mixtures thereof.

In other non-limiting embodiments, the present invention provides a poly (urethane urea) composition comprising:

(a) at least one poly (urethane urea) containing a reaction product of components including:

(i) at least one isocyanate functional urethane prepolymer containing the reaction product:

1. The first amount of at least one polyisocyanate and

2. The first amount of at least one branched polyol; and

(ii) water

with the formation of a urethane urea prepolymer with isocyanate functionality;

(b) a second amount of at least one polyisocyanate and a second amount of at least one branched polyol; and

(c) at least one reinforcing material selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites and mixtures thereof.

In some non-limiting embodiments, the present invention provides methods for producing an enhanced polyurethane composition, which comprises the steps of: mixing a solution of a precursor of a reaction product of components of the above-described polyurethane or poly (urethane urea) with a precursor of nanostructures; the formation of nanostructures from the precursor of nanostructures in the polyurethane matrix and the polymerization of the precursor of the reaction product of the components with the formation of polyurethane.

R group

In some non-limiting embodiments, the present invention provides a laminate comprising:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

In other non-limiting embodiments, the present invention provides a laminate comprising:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate;

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(iii) at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or a combination thereof; and

(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

In other non-limiting embodiments, the present invention provides a laminate comprising:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) a prepolymer, which is a reaction product of components including:

(1) at least one polyisocyanate;

(2) at least one polycaprolactone polyol; and

(3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof; and

(ii) at least one diol containing from 2 to 18 carbon atoms; and

(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

In other non-limiting embodiments, the present invention provides a laminate comprising:

(a) at least one layer of at least one polyurethane containing the reaction product of components including:

(i) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate or branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and

(ii) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; and

(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

In other non-limiting embodiments, the present invention provides a laminate comprising:

(a) at least one layer of at least one poly (urethane urea) containing the reaction product of components including:

(i) at least one prepolymer with isocyanate functionality containing the reaction product:

1. At least one polyisocyanate and

2. Water; and

(ii) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups;

where these components are essentially free of amine curing agent; and

(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

In other non-limiting embodiments, the present invention provides a laminate comprising:

(A) at least one layer of at least one poly (urethane urea) containing a reaction product of components including:

(a) at least one urethane-urea prepolymer with isocyanate functionality, containing the reaction product of components including:

(1) at least one urethane prepolymer with isocyanate functionality containing the reaction product:

but. The first amount of at least one polyisocyanate and

b. A first amount of at least one branched polyol; and

(2) water;

with the formation of a urethane urea prepolymer with isocyanate functionality and

(b) a second amount of at least one polyisocyanate and a second amount of at least one branched polyol; and

(B) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, masonry, fabric, metal or organic polymeric material, and combinations thereof.

The present invention also provides cured compositions, products, laminates and methods for producing and using compositions, products and laminates containing the polyurethanes and poly (urethane ureas) described above.

BRIEF DESCRIPTION OF THE DRAWINGS

The above summary of the invention, as well as the following detailed description, is easier to understand when considering the accompanying drawings.

FIGURE 1 is a graph of G 'and G' 'as a function of temperature when measured using dynamic mechanical analysis (DMA), and this graph shows the dynamic modulus, loss modulus and tangential delta (tan Delta) for casting in polyurethane in accordance with example A, formulation 1 of the present invention;

FIGURE 2 is a graph of G 'and G' 'as a function of temperature when measured using dynamic mechanical analysis (DMA, DMA), and this graph shows the dynamic modulus, loss modulus and tan Delta for polyurethane casting in accordance with example A Formulation 2 of the present invention;

FIGURE 3 is a graph of G 'and G' 'as a function of temperature when measured using dynamic mechanical analysis (DMA), and this graph shows the dynamic modulus, loss modulus and tan Delta for polyurethane casting in accordance with Example A formulation 40 of the present invention;

FIG. 4 is a TEM photomicrograph showing a polyurethane casting in accordance with Example A, Formulation 2, analyzed two weeks after preparation in accordance with the present invention;

FIG. 5 is a TEM photomicrograph showing a polyurethane casting according to Example A, Formulation 2 analyzed three weeks after being prepared in accordance with the present invention; FIG.

FIG.6 is a TEM micrograph showing a polyurethane casting according to Example A, Formulation 2, analyzed seven months after being prepared in accordance with the present invention;

FIG.7 is an electronic diffraction pattern of a polyurethane casting of Example A, Formulation 2 with FIG.6;

FIG. 8 is a TEM photomicrograph showing the second part of the polyurethane casting of FIG. 6 in accordance with Example A, formulation 2 obtained after aging under normal conditions for approximately seven months in accordance with the present invention;

FIGURE 9 is a TEM photomicrograph showing the first part of a polyurethane casting according to Example A, Formulation 2, obtained after incubation at room temperature for about two to four weeks;

FIGURE 10 is a TEM photomicrograph showing the second part of a polyurethane casting according to Example A, formulation 2 shown in FIG. 9;

11 is a TEM micrograph showing a polyurethane casting in accordance with example A, formulation 2;

12 is a TEM photomicrograph showing the first part of a polyurethane casting according to Example A, Formulation 2, obtained after incubation at room temperature for approximately seven months;

FIGURE 13 is a TEM photomicrograph showing the second part of a polyurethane casting according to Example A, formulation 2 shown in FIG. 12;

FIG. 14 is a graph of heat flux as a function of temperature when measured using differential scanning calorimetry (DSC) for polyurethane castings in accordance with Example A, Formulation 2, measured after aging under normal conditions for two weeks, three months, and seven months, respectively, in accordance with the present invention;

FIG. 15 is a graph of Gardner impact resistance as a function of Young's modulus for polyurethane castings in accordance with Example A, Formulations 1 and 2, measured after aging under normal conditions for seven months and one year, respectively, in accordance with the present invention;

FIG. 16 is a graph of dynamic elastic modulus, loss modulus, and tan Delta as a function of temperature measured using DMA for polyurethane castings obtained in accordance with Example A formulation 114 in accordance with the present invention;

FIGURE 17 is a perspective photograph of a test sample of formulation 2, Example A, after firing a sample of 0.40 caliber bullets from a distance of 30 feet (9.2 m) at a speed of 987 ft / s (300.8 m / s);

FIG. 18 is a front view photograph of a test sample of Formulation 2, Example A, after firing a sample with a 12 gauge shotgun from a distance of 20 feet (6.1 m) at a speed of 1290 ft / s (393.2 m / s) using heavy sports lead pellets;

FIGURE 19 is a photograph of the front view of the test sample of formulation 93, Example A, after firing the sample with 9 mm bullets from a distance of 20 feet (6.1 m) at an initial speed of 1350 ft / s (411.5 m / s);

FIGURE 20 is a perspective photograph of a test sample of formulation 94, Example A, after firing a sample with a 9 mm bullet from a distance of 20 feet (6.1 m) at an initial speed of 1350 ft / s (411.5 m / s);

FIGURE 21 is a side view of the sample shown in FIGURE 20;

FIG 22 is a front view of a portion of the composite in accordance with the present invention after firing a sample with four 7.62 × 39 mm bullets having a steel core from an AK-47 rifle from a distance of 30 yards (27.4 m) at an initial speed of 2700 ft / s (823 m / s);

FIGURE 23 is a rear view of the sample of FIG.22;

FIG. 24 is a graph of heat flux as a function of temperature when measured using differential scanning calorimetry (DSC) for polyurethane castings in accordance with Example A, Formulation 2, of the present invention;

FIGURE 25 is a graph of heat flux as a function of temperature when measured using DSC for castings made of polyurethane obtained in accordance with example A, formulation 136, of the present invention;

FIG. 26 is a graph of mass loss as a function of temperature when measured using thermogravimetric analysis (TGA, TGA) for polyurethane castings obtained in accordance with Example A Formulation 136 of the present invention.

DETAILED DESCRIPTION

Used in this description, spatial definitions or definitions of direction, such as "inside", "left", "right", "up", "down", "horizontal", "vertical", etc., relate to the invention as follows as described in it. However, it should be understood that the invention may allow various alternative orientations and, accordingly, such definitions should not be construed as limiting. For the purposes of the present description, unless otherwise indicated, all numbers expressing the amounts of ingredients, reaction conditions, sizes, physical characteristics, etc. used in the description and in the claims should be understood as modified in all cases by the definition of “approximately ". Accordingly, unless otherwise indicated, the numerical parameters presented in the following description and in the attached claims are approximations that can vary depending on the desired properties, which are believed to be obtained using the present invention. In an extreme case, but not as an attempt to limit the application to a system of equivalents of the scope of the claims, each numerical parameter should at least be construed taking into account the number of significant characters represented and through the use of conventional rounding techniques.

Although the numerical ranges and parameters establishing a wide scope of the invention are approximations, the numerical values indicated in the specific examples are presented as accurately as possible. Any numerical values, however, internally contain some errors that inevitably arise from the standard deviation inherent in the corresponding test measurements.

In addition, it should be understood that the numerical ranges given herein are intended to include all the sub-ranges within them. For example, the interval “from 1 to 10”, as implied, includes any and all sub-intervals between the specified minimum value of 1 and the specified maximum value of 10, including these values; that is, all subintervals starting with a minimum value equal to or greater than 1 and ending with a maximum value equal to or less than 10, and all subintervals between them, for example from 1 to 6.3, from 5.5 to 10, or from 2 , 7 to 6.1.

“Alkyl” means an aliphatic hydrocarbon group which may be linear or branched and may contain from about 1 to about 20 carbon atoms in a chain. Non-limiting examples of suitable alkyl groups in the chain contain from about 1 to about 18 carbon atoms or from about 1 to about 6 carbon atoms in the chain. “Branched” means that one or more lower alkyl groups, such as methyl, ethyl or propyl, are attached to a linear alkyl chain. “Lower alkyl” or “short chain alkyl” means a group containing from about 1 to about 6 carbon atoms in a chain, which may be linear or branched. "Alkyl" may be unsubstituted or optionally substituted with one or more substituents, which may be the same or different, each substituent independently selected from the group consisting of halogen atom, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, - NH (alkyl), -NH (cycloalkyl), -N (alkyl) ₂ , carboxy and

-C (O) O-alkyl. Non-limiting examples of suitable alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl.

“Alkylene” means a bifunctional group obtained by removing a hydrogen atom from an alkyl group as defined above. Non-limiting examples of alkylene are methylene, ethylene, and propylene.

“Aryl” means an aromatic monocyclic or polycyclic ring system containing from about 6 to about 14 carbon atoms or from about 6 to about 10 carbon atoms. An aryl group may optionally be substituted with one or more “ring system substituents”, which may be the same or different and which have the meanings defined herein. Non-limiting examples of suitable aryl groups are phenyl and naphthyl.

“Heteroaryl” means an aromatic monocyclic or polycyclic ring system containing from about 5 to about 14 carbon atoms in the ring or from about 5 to about 10 atoms in the ring, in which one or more ring atoms are an element other than a carbon atom, for example an atom of nitrogen, oxygen or sulfur, alone or in combination. In some non-limiting embodiments, heteroaryls contain from about 5 to about 6 atoms in the ring. “Heteroaryl” may optionally be substituted with one or more “ring system substituents”, which may be the same or different and which have the meanings defined in this description. The prefix aza, oxa or thia before the root name of heteroaryl means that at least one nitrogen, oxygen or sulfur atom is respectively present as a ring atom. The nitrogen atom of heteroaryl may optionally be oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryls are pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-substituted pyridones), isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazol, 1,2-pyrazol, thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, phthalazinyl, oxindolyl, imidazo [1,2-a] pyridinyl, imidazo [2,1-b] thiazolyl, benzofurazanil, indolyl, azainindolyl, benzimidazolyl, benzothienyl, thiinolinyl, quinolinyl thienopyrimidyl, pyrrolopyridyl, imidazopyridyl, and ohinolinil, benzoazaindolil, 1,2,4-triazinyl, benzothiazolyl, etc. The term “heteroaryl” also refers to partially saturated heteroaryl residues, such as, for example, tetrahydroisoquinolyl, tetrahydroquinolyl, etc.

“Aralkyl” or “arylalkyl” means an arylalkyl group in which aryl and alkyl are as previously described. In some non-limiting embodiments, the implementation of aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups are benzyl, 2-phenethyl and naphthalenylmethyl. The bond with the main residue is via alkyl.

“Alkylaryl” means an alkylaryl group in which alkyl and aryl are as previously defined. In some non-limiting embodiments, the implementation of alkylaryls include lower alkyl groups. A non-limiting example of a suitable alkylaryl group is tolyl. Communication with the main residue is via aryl.

“Cycloalkyl” means a non-aromatic mono- or polycyclic ring system containing from about 3 to about 10 carbon atoms or from about 5 to about 10 carbon atoms. In some non-limiting embodiments, the implementation of the cycloalkyl ring contains from about 5 to about 7 atoms in the ring. Cycloalkyl may optionally be substituted with one or more “ring system substituents,” which may be the same or different and which are as defined above. Non-limiting examples of suitable monocyclic cycloalkyls are cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Non-limiting examples of suitable polycyclic cycloalkyls are 1-decalinyl, norbornyl, adamantyl, etc.

"Halogen atom" or "halogen" means fluorine, chlorine, bromine or iodine. In some non-limiting embodiments, halogen groups are fluoro, chloro or bromo.

“Substituent ring system” means a substituent connected to an aromatic or non-aromatic ring system, which, for example, replaces an available hydrogen atom in the ring system. Ring system substituents may be the same or different, each of which is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, alkylaryl, heteroaralkyl, heteroarylalkenyl, heteroarylalkynyl, alkylheteroaryl, hydroxy, hydroxyalkyl, alkoxyoxyryl , acyl, aroyl, halogen, nitro, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylthio, arylthio, heteroarylthio, aralkylthio, heteroalkyl , Heterocyclyl, -C (= N-CN) -NH _2, -C (= NH) -NH _2, -C (= NH) -NH (alkyl), Y ₁ Y ₂ N-, Y ₁ Y ₂ N- alkyl, Y ₁ Y ₂ NC (O) -, Y ₁ Y ₂ NSO ₂ - and -SO ₂ NY ₁ Y ₂ , where Y ₁ and Y ₂ may be the same or different and independently selected from the group comprising a hydrogen atom, alkyl , aryl, cycloalkyl and aralkyl. A “ring system substituent” can also mean a single residue that simultaneously replaces two available hydrogen atoms on two adjacent carbon atoms (one H on each carbon atom) in the ring system. Examples of such residues are methylenedioxy, ethylenedioxy, —C (CH ₃ ) ₂ - etc., which form residues such as, for example:

“Heterocyclyl” means a non-aromatic saturated monocyclic or polycyclic ring system containing from about 3 to about 10 atoms in the ring or from about 5 to about 10 atoms in the ring, in which one or more atoms of the ring system is an element other than a carbon atom, for example, a nitrogen, oxygen or sulfur atom, individually or in combination. There are no adjacent oxygen and / or sulfur atoms in this ring system. In some non-limiting embodiments, heterocyclyl contains from about 5 to about 6 atoms in the ring. The prefix aza-, oxa- or thia- before the root name of the heterocyclyl means that at least one nitrogen, oxygen or sulfur atom is respectively present as a ring atom. Any —NH moiety in the heterocyclyl ring may be protected by groups such as, for example, —N (Boc), —N (CBz), —N (Tos), etc .; such protection is also considered as part of this invention. Heterocyclyl may optionally be substituted with one or more ring system substituents, which may be the same or different and which have the meanings defined above. The nitrogen or sulfur atom of the heterocyclyl may optionally be oxidized to the corresponding N-oxide, S-oxide or S, S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings are piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, lactam, lactone, etc.

It should be noted that in the ring systems of the present invention containing heteroatoms, there are no hydroxyl groups on carbon atoms adjacent to N, O or S atoms, and there are no N or S groups on carbon atoms adjacent to another heteroatom. That is, for example, in the ring:

there is no —OH group attached directly to the carbon atoms indicated by 2 and 5.

It should also be noted that tautomeric forms, such as, for example, fragments:

in some embodiments, are considered equivalent.

“Heteroaralkyl” means a heteroarylalkyl group in which heteroaryl and alkyl are as previously described. In some non-limiting embodiments, heteroalkyl contains a lower alkyl group. Non-limiting examples of suitable heteroalkyl groups include pyridylmethyl and quinolin-3-ylmethyl. The bond with the main residue is via alkyl.

“Hydroxyalkyl” means a HO-alkyl group in which alkyl is as previously defined. In some non-limiting embodiments, hydroxyalkyl contains a lower alkyl group. Non-limiting examples of suitable hydroxyalkyl groups include hydroxymethyl and 2-hydroxyethyl.

“Alkoxy” means an alkyl-O-group in which the alkyl group is as previously described. Non-limiting examples of suitable alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The bond with the main residue is via an etheric oxygen atom.

“Aryloxy” means an aryl-O-group in which the aryl group is as previously described. Non-limiting examples of suitable aryloxy groups are phenoxy and naphthoxy. The bond with the main residue is via an etheric oxygen atom.

“Alkylthio” means an alkyl-S-group in which the alkyl group is as previously described. Non-limiting examples of suitable alkylthio groups are methylthio and ethylthio. The bond with the main residue is via a sulfur atom.

“Arylthio” means an aryl-S group in which the aryl group is as previously described. Non-limiting examples of suitable arylthio groups are phenylthio and naphthylthio. The bond with the main residue is via a sulfur atom.

“Aralkylthio” means an aralkyl-S-group in which the aralkyl group is as previously described. A non-limiting example of a suitable aralkylthio group is benzylthio. The bond with the main residue is via a sulfur atom.

“Alkoxycarbonyl” means an alkyl-O — CO— group. Non-limiting examples of suitable alkoxycarbonyl groups are methoxycarbonyl and ethoxycarbonyl. The bond with the main residue is via carbonyl.

“Aryloxycarbonyl” means an aryl-O — C (O) group. Non-limiting examples of suitable aryloxycarbonyl groups are phenoxycarbonyl and naphthoxycarbonyl. The bond with the main residue is via carbonyl.

“Aralkoxycarbonyl” means an aralkyl-O — C (O) group. A non-limiting example of a suitable aralkoxycarbonyl group is benzyloxycarbonyl. The bond with the main residue is via carbonyl.

“Alkylsulfonyl” means an alkyl-S (O ₂ ) group. In some non-limiting embodiments, the alkylsulfonyl group contains a lower alkyl group. Communication with the main residue is carried out through sulfonyl.

“Arylsulfonyl” means an aryl-S (O ₂ ) group. Communication with the main residue is carried out through sulfonyl.

The term “substituted” means that one or more hydrogen atoms on the desired atom is substituted by selection from the indicated group, provided that the normal valency of the designated atom is not exceeded in existing cases and that substitution leads to a stable compound. Combinations of substituents and / or variables are permissible only if such combinations result in stable compounds.

The term “optionally substituted” means optionally substituted with certain groups, radicals or residues.

It should be understood that any carbon atom, as well as a heteroatom with unfilled valencies in the text, diagrams, examples and tables, as implied, has a sufficient number of hydrogen atoms to complement the valencies.

When a functional group in a compound is called “protected”, this means that the group is in a modified form to prevent undesirable side reactions at the protected site when the compound is reacted. Suitable protecting groups can be determined by those skilled in the art, as well as using standard textbooks such as, for example, TW Greene et al., Protective Groups in Organic Synthesis (1991), Wiley, New York.

When any variable (for example, aryl, heterocycle, R ² , etc.) occurs more than once in any component, its definition in each case does not depend on its definition in every other case.

As used herein, the term “composition” is intended to encompass a product containing certain ingredients in certain amounts, as well as any product that is directly or indirectly a combination of certain ingredients in certain quantities.

Used in this case, the expression “formed from” or “obtained from” means an open wording, such as, for example, “comprising”. By itself, this expression implies that the composition "formed from" or "obtained from" a list of these components will be a composition containing at least these listed components or a reaction product of at least these listed components and may further include other, non-listed components during the formation or preparation of the composition. Used in this case, the expression "reaction product" means the product (s) of a chemical reaction of the listed components and may include products of an incomplete reaction, as well as products of a complete reaction.

As used herein, the term “polymer” is intended to encompass oligomers and includes, without limitation, both homopolymers and copolymers. The term “prepolymer” means a compound, monomer or oligomer used to make a polymer, and includes, but is not limited to, oligomers of both a homopolymer and a copolymer.

The term "thermoplastic polymer" means a polymer that becomes liquid when heated and can be soluble in solvents.

The term "thermosetting polymer" means a polymer that cures or "sets" upon curing or crosslinking. After curing, the crosslinked thermosetting polymer will not melt when exposed to heat and, as a rule, is insoluble in solvents.

As used herein, the term “cure” as applied to a composition, for example, “composition when it is cured” or “cured composition”, will mean that any curable or crosslinkable components of the composition are at least partially cured or crosslinked. In some non-limiting embodiments of the present invention, the crosslink density of the crosslinkable components, i.e., the degree of crosslinking, is in the range of from about 5% to about 100% of the total crosslinking. In other non-limiting embodiments of the present invention, the crosslinking density is in the range of from about 35% to about 85% of the total crosslinking. In other non-limiting embodiments of the present invention, the crosslinking density is in the range of from about 50% to about 85% of the total crosslinking. A person skilled in the art will understand that the presence and degree of crosslinking, that is, the crosslinking density, can be determined using a variety of methods, such as dynamic mechanical thermal analysis (DMA) using a TA Instruments DMA 2080 DMA analyzer within the temperature range the interval from -65 ° F (-18 ° C) to 350 ° F (177 ° C), conducted in a nitrogen atmosphere in accordance with ASTM-D 4065-01. In this method, the glass transition temperature and the crosslink density of free films of coatings or polymers are determined. Such physical properties of the cured material are related to the structure of the crosslinked polymer network. In one embodiment of the present invention, the cure adequacy is evaluated by the solvent resistance of the cured polymer film. For example, solvent resistance can be measured by determining the number of double acetone rubs. For the purposes of the present invention, the coating is believed to be “cured” when the film can withstand at least 100 double wipes with acetone without significantly softening the film and without removing the film.

The curing of the polymerizable composition can be obtained by exposing the composition to curing conditions, such as, but not limited to, thermal curing, irradiation, etc., resulting in a reaction between the reactive groups of the composition and resulting in polymerization and formation of a solid polymerizate. When the polymerizable composition is subjected to curing conditions, after polymerization and after the interaction of most reactive groups, the reaction rate of the remaining unreacted reactive groups is gradually slowed down. In some non-limiting embodiments, the polymerizable composition may be subjected to curing conditions until it is at least partially cured. The term "at least partially cured" means the effect on the polymerizable composition of the curing conditions where the reaction of at least part of the reactive groups of the composition to form a solid polymerizate. At least partially cured polymerizate can be removed from the mold and used, for example, to prepare products, such as windows, cut into pieces for testing or subjected to mechanical operations, such as processing into optical lenses. In some non-limiting embodiments, the polymerizable composition may be subjected to curing conditions such that substantially complete cure is achieved, and in this case, additional exposure to the curing conditions does not result in a significant additional improvement in polymer properties such as strength or hardness.

The term “polyurethane” is intended to include not only polyurethanes that are formed by the reaction of polyisocyanates and polyols, but also poly (urethane ureas) that are obtained by the reaction of polyisocyanates with polyols and water and / or polyamines.

The polyurethanes and poly (urethane ureas) of the present invention can be used in such cases in which one or more of the following properties is required: transparency, high optical characteristics, high Abbe number, low staining, energy absorption, stiffness, moisture resistance, UV resistance light, weather resistance, low water absorption, hydrolytic stability and resistance to pool or explosion.

In some embodiments of the invention, cured articles made from the polyurethanes and poly (urethane ureas) of the present invention are usually transparent, can have a light transmission of at least about 80%, a haze of less than about 2%, and do not show visible changes after exposure to light and water within 1000 hours in accordance with ASTM-D 1499-64.

The polyurethanes and poly (urethane ureas) of the present invention can be converted into articles having various shapes and sizes, such as flat sheets or curved sheets. Non-limiting examples of acceptable methods for producing products are heat treatment, injection molding, or pouring liquid polyurethane or poly (urethane urea) into a mold and curing the product to form a molded product.

Typically, the polyurethanes or poly (urethane ureas) of the present invention contain a reaction product of components comprising at least one polyisocyanate and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 or, at least 3 hydroxyl groups, where at least one of the polyisocyanate (s) and / or aliphatic (s) polyol (s) is branched (s).

In the present invention, at least one isocyanate and / or at least one polyol are branched. Used in this case, the definition of "branched" means a chain of atoms with one or more side chains attached to it. Branching is carried out by substituting a substituent, for example a hydrogen atom, with a covalently bonded substituent or a residue, for example an alkyl group. Without being tied to any theory, it is believed that the branching of the polyisocyanate and / or polyol can increase the free volume within the polymer matrix, as a result of which space is created for the movement of molecules. The molecules can orient and rotate in configurations and arrangements having preferred energy states, which can provide good impact properties and / or a high modulus of elasticity for the cured polymer matrix. As shown in FIGS. 1, 2 and 3, the dynamomechanical analysis (DMA) of polyurethane castings prepared in accordance with Examples 1, 2 and 40, respectively, for the loss modulus as a function of temperature shows a low phase transition temperature at approximately −70 ° C. DMA is carried out in the temperature range from -65 ° F (-18 ° C) to 350 ° F (177 ° C) in a nitrogen atmosphere in accordance with ASTM-D 4065-01. Without being tied to any theory, it is believed that the low phase transition temperature is due to molecular torsion mobility at this temperature and is believed to contribute to the high toughness of such polymers.

When a viscoelastic material is subjected to vibrational vibration, a certain amount of energy is accumulated in the polymer, which is proportional to the elastic component of the modulus G 'or dynamic modulus of elasticity, and a certain amount of energy is converted into heat through internal friction or viscous dispersion, which is expressed in the value of the loss modulus G' '. The maximum value of the loss modulus is denoted by tan Delta, which is the maximum internal friction, damping, or viscous energy dissipation.

Glassy polymers with high light transmittance rarely exhibit high impact strength. Polycarbonate plastics such as LEXAN may exhibit a similar low phase transition temperature, but may have lower toughness and lower Young's modulus.

The physical properties of the polyurethanes and poly (urethane ureas) of the present invention are obtained from their molecular structure and are determined by the choice of structural blocks, for example, the choice of reagents, the ratio of hard crystalline and soft amorphous segments and supramolecular structures due to atomic interactions between chains.

Rigid segments, i.e. crystalline and semi-crystalline regions of the urethane polymer, are formed by the reaction of an isocyanate and a chain extender, such as an aliphatic polyol containing from 4 to 18 carbon atoms, or a low molecular weight polyol having a molecular weight of less than about 200, which are discussed in this description. Typically, a soft segment, i.e. an amorphous rubbery region of a urethane polymer, is formed by the reaction of an isocyanate and a polymer backbone component, for example a polyester polyol (such as a polycarbonate polyol), or a polyether polyol, or short chain diols that do not form crystalline regions.

The qualitative contribution of a particular organic polyol to either the hard or soft segment when it is mixed and reacted with other polyurethane-forming components can be easily determined by measuring the Fischer microhardness of the resulting cured polyurethane in accordance with ISO 14577-1: 2002 .

In some non-limiting embodiments, the implementation of the hard segments in the polyurethane areas is in the range from about 10 wt.% To about 100 wt.%, Or from about 50 wt.% To about 100 wt.%, Or from about 70 wt.% To about 100 wt.%. The content of hard segments is the mass percentage of bonds of hard segments present in the polymer, and can be calculated by determining the total number of equivalents, and from this the total mass of all reagents, and dividing the total mass of bonds of hard segments that can be obtained from these reagents by the total the mass of the reagents themselves. The following example further explains this calculation. In example 1, formulation 1, which follows, a polyurethane product in accordance with the present invention is obtained by introducing into the reaction 0.7 equivalent of 1,4-butanediol, 0.3 equivalent of trimethylolpropane and one equivalent of 4,4'-methylene bis ( cyclohexyl isocyanate) (DESMODUR W). The equivalent mass of 1,4-butanediol is 45 g / equiv., The equivalent weight of trimethylolpropane is 44.7 g / equiv. (corrected for impurities) and the equivalent mass of DESMODUR W is 131.2 g / equiv. Therefore, the actual weight of the ingredients used is 31.54 parts by weight. 1,4-butanediol, 13.2 parts by weight trimethylolpropane and 131.2 parts by weight DESMODUR W, or the total mass of reagents is 175 parts by weight. One equivalent of 1,4-butanediol will give one equivalent of the bond of the hard segment, where the bond of the hard segment is a 1,4-butanediol / DESMODUR W dimer. The equivalent bond mass of the 1,4-butanediol / DESMODUR W dimer is 176 g / equiv. so that the total bond mass of the hard segments determined by multiplying the equivalent mass of the dimer of the hard segments by the number of equivalents of 1,4-butanediol will be 123.2 g / equiv. Therefore, the total bond mass of the 1,4-butanediol / DESMODUR W dimer, 123.2, divided by the total mass of reagents, 175.7, multiplied by 100 for conversion to percent, will give a mass percent bond of the hard segment of 70 wt.%.

Both Plexiglas and elongated acrylic polymer absorb a huge amount of water from the atmosphere. In accelerated tests, such as QUV-B or soaking in water at room temperature, polyurethanes in accordance with the present invention, including short-chain diols, such as butanediol and pentanediol, unexpectedly essentially do not absorb water when studying the rate of passage of water vapor and after soaking in water for about 24 hours. Without being attached to any theory, it is believed that even if these plastics are polar, the hydrogen bonding in the domains of hard segments is strong enough to block the passage of water vapor and water absorption. In comparison, an elongated acrylic polymer will absorb enough water to cause the plastic to swell violently to the point where it cracks in the plane, like onion peel layers, peeling off until it falls off. Low water absorption can also mitigate any degradation due to hydrolysis of urethane groups in the polymer.

A discussion of the various aspects and embodiments of the polyurethanes and poly (urethane ureas) of the present invention is divided into groups, typically A-Q, below. As indicated above, this grouping is not intended to limit the scope of the invention, and aspects of one group may be related to objects of the invention of other groups. In addition, limiting the amounts of reagents in one group does not necessarily imply limiting the amounts of the same component in other groups, although the corresponding amounts may be the same for different groups, unless otherwise noted.

Group A

In some non-limiting embodiments, the implementation of the present invention provides polyurethanes containing a reaction product of components, including:

(a) about 1 equivalent of at least one polyisocyanate;

(b) from about 0.05 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(c) from about 0.1 to about 0.95 equivalents of at least one diol containing from 2 to 18 carbon atoms;

where said components are substantially free of polyester polyol and polyether polyol, and where the reaction components are held at a temperature of at least about 100 ° C. for at least about 10 minutes.

Used in this case, the definition of "equivalent" means the mass of a substance in grams that will react with one mole (6.022 × 10 ²³ electrons) of another substance. Used in this case, the definition of "equivalent mass" is actually equal to the amount of substance in moles divided by the valency or number of functional reactive groups of the substance.

Used in this case, the definition of "isocyanate" includes compounds, monomers, oligomers and polymers containing at least one or at least two -N = C = O functional groups and / or at least one or, at least two —N = C = S (isothiocyanate) groups. Monofunctional isocyanates can be used as chain terminating agents or to create end groups during polymerization. As used herein, the term “polyisocyanate” means an isocyanate containing at least two —N = C = O functional groups and / or at least two —N = C = S (isothiocyanate) groups, such as diisocyanates or triisocyanates, as well as dimers and trimers or biurets of isocyanates discussed in this description. Suitable isocyanates are capable of forming a covalent bond with a reactive group, such as a hydroxyl, thiol or amine functional group. Isocyanates that can be used in the present invention can be branched or unbranched. As discussed above, the use of branched isocyanates may be desirable in order to increase the free volume inside the polymer matrix in order to create space for the movement of molecules.

Isocyanates that can be used in the present invention include “modified”, “unmodified” and mixtures of “modified” and “unmodified” isocyanates. Isocyanates may have “free”, “blocked” or partially blocked isocyanate groups. The term “modified” means that the aforementioned isocyanates are modified in a known manner to introduce biuret, urea, carbodiimide, urethane or isocyanurate groups or blocking groups. In some non-limiting embodiments of the invention, a “modified” isocyanate is prepared by cycloaddition processes to produce dimers and trimers of an isocyanate, i.e., polyisocyanates. Free isocyanate groups are extremely reactive. To control the reactivity of the components containing the isocyanate group, the NCO groups can be blocked with some selected organic compounds, which makes the isocyanate group inert to compounds with reactive hydrogen at room temperature. When heated to elevated temperatures, for example in the range of from about 90 ° C to about 200 ° C, blocked isocyanates release the blocking agent and react in the same way as the original unblocked or free isocyanate.

Typically, the compounds used to block isocyanates are organic compounds that have active hydrogen atoms, for example volatile alcohols, epsilon-caprolactam or ketoxime compounds. Non-limiting examples of suitable blocking compounds are phenol, cresol, nonylphenol, epsilon-caprolactam, and methyl ethyl ketoxime.

As used herein, NCO with respect to NCO: OH means a free isocyanate of materials containing free isocyanate, and blocked or partially blocked isocyanate-containing materials after the release of the blocking agent. In some cases it is not possible to remove the entire blocking agent. In such situations, it is necessary to use more blocked isocyanate-containing material in order to obtain the desired level of free NCO group.

The molecular weight of the isocyanate and isothiocyanate can vary widely. In alternative non-limiting embodiments, the number average molecular weight (Mn) of each may be at least about 100 g / mol, or at least about 150 g / mol, or less than about 15000 g / mol, or less than about 5000 g / mol. The number average molecular weight can be determined using known methods, such as gel permeation chromatography (GPC, GPC) using polystyrene standards.

Non-limiting examples of suitable isocyanates are aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, their dimers and trimers, and mixtures thereof. Useful cycloaliphatic isocyanates are isocyanates in which one or more isocyanate groups are directly attached to the cycloaliphatic ring, and cycloaliphatic isocyanates in which one or more isocyanate groups are not directly attached to the cycloaliphatic ring. Useful aromatic isocyanates are isocyanates in which one or more isocyanate groups are attached directly to the aromatic ring, and aromatic isocyanates in which one or more isocyanate groups are not attached directly to the aromatic ring. Useful heterocyclic isocyanates are isocyanates in which one or more isocyanate groups are attached directly to the heterocyclic ring, and heterocyclic isocyanates in which one or more isocyanate groups are not attached directly to the aromatic ring.

Cycloaliphatic diisocyanates are desirable for use in the present invention since they are not adversely affected by ultraviolet radiation, and they can produce polyurethanes having high levels of shock energy absorption, which makes them attractive for glass replacement and for use in safety glass. In addition, polyurethanes prepared with cycloaliphatic diisocyanates are not adversely affected by normal process temperatures. When using aromatic polyisocyanates, as a rule, you should carefully approach the choice of material that does not cause coloring of the polyurethane (for example, yellow).

In some non-limiting embodiments, the implementation of aliphatic and cycloaliphatic diisocyanates may contain from about 6 to about 100 carbon atoms, connected in a linear chain or cyclized and having two isocyanate reactive end groups.

Non-limiting examples of suitable aliphatic isocyanates are linear isocyanates such as ethylenediisocyanate, trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, hexamethylene diisocyanate diane cyanodiene, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether.

Other non-limiting examples of suitable aliphatic isocyanates include branched isocyanates such as trimethylhexanediisocyanate, trimethylhexamethylene diisocyanate (TMDI), 2,2'-dimethylpentanediisocyanate, 2,2,4-trimethylhexanediisocyanate, 2,4,4-trimethyldianisomethyxate (isocyanatomethyl) octane, 2,5,7-trimethyl-1,8-diisocyanato-5- (isocyanatomethyl) octane, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, methyl ester of lysine diisocyanate and methyl ester of lysine triisocyanate.

Non-limiting examples of suitable cycloaliphatic isocyanates are binuclear compounds linked by a bridge using an isopropylidene group or an alkylene group of 1-3 carbon atoms. Non-limiting examples of suitable cycloaliphatic isocyanates are 1,1'-methylene bis (4-isocyanatocyclohexane) or 4,4'-methylene bis (cyclohexyl isocyanate) (e.g. DESMODUR W, commercially available from Bayer Corp., Pittsburgh, PA), 4 , 4'-isopropylidene bis (cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate (CHDI), 4,4'-dicyclohexyl methanediisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (branched isocyanate, also known as isophorondi which is commercially available from Arco Chemical Co., Newtown Square, Pennsylvania, and meta-t etramethylxylene diisocyanate (branched isocyanate, also known as 1,3-bis (1-isocyanato-1-methylethyl) benzene, which is commercially available from Cytec Industries Inc., West Patterson, New Jersey, under the trade name TMXDI ^® (Meta) Aliphatic Isocyanate ), as well as mixtures thereof.

Other useful binuclear cycloaliphatic diisocyanates include isocyanates formed through an alkylene group of 1 to 3 carbon atoms inclusive, and which may be substituted with a nitro group, chlorine, alkyl, alkoxy group and other groups that do not react with hydroxyl groups (or with active hydrogen atoms), provided that they are not arranged to convert an isocyanate group into a non-reactive group. In addition, hydrogenated aromatic diisocyanates such as hydrogenated toluene diisocyanate can be used. Binuclear diisocyanates may also be used in which one ring is saturated and the other unsaturated, which are obtained by partial hydrogenation of aromatic diisocyanates, such as diphenylmethanediisocyanates, diphenylisopropylidene diisocyanate and diphenylenediisocyanate.

Mixtures of cycloaliphatic diisocyanates with aliphatic diisocyanates and / or aromatic diisocyanates may also be used. For example, 4,4'-methylene bis (cyclohexyl isocyanate) can be used with industrial mixtures of isomers of toluene diisocyanate or meta-phenylenediisocyanate.

Thioisocyanates corresponding to the above diisocyanates as well as mixed compounds containing both an isocyanate and a thioisocyanate group can be used.

Non-limiting examples of suitable isocyanates may include, but are not limited to, DESMODUR W, DESMODUR N 3300 (hexamethylene diisocyanate trimer), DESMODUR N 3400 (60% hexamethylene diisocyanate dimer, and 40% hexamethylene diisocyanate dimer), which are commercially available from Bayer.

In some non-limiting embodiments of the invention, the isocyanate may be 1,1'-methylene bis (4-isocyanatocyclohexane) (also known as 4,4'-methylene bis (cyclohexyl isocyanate)) and isomeric mixtures thereof. Used in this case, the definition of "isomeric mixture" refers to a mixture of cis-cis, trans-trans and cis-trans isomers of isocyanate. Non-limiting examples of isomeric mixtures suitable for use in the present invention may be the trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate), hereinafter referred to as "PICM" (para-isocyanatocyclohexylmethane), the cis-trans isomer PICM, cis- cis isomer of PICM and mixtures thereof. Three suitable for use in the present invention isomers of 4,4'-methylene bis (cyclohexyl isocyanate) (also known as 1,1'-methylene bis (4-isocyanatocyclohexane)) are presented below.

In some non-limiting embodiments of the invention, the PICM used in the present invention can be obtained by phosgenation of 4,4'-methylene bis (cyclohexylamine) (PACM) according to methods well known in the art, for example, according to the methods described in US patent No. 2644007 and 2680127, which are incorporated by reference. Mixtures of PACM isomers upon phosgenation can give PICM in the liquid phase, partially in the liquid phase or in the solid phase at room temperature. Mixtures of PACM isomers can be obtained by hydrogenation of methylenedianiline and / or by fractional crystallization of a mixture of PACM isomers in the presence of water and alcohols, such as methanol and ethanol.

In some non-limiting embodiments of the invention, the isomeric mixture may contain from about 10 to about 100 wt.% The trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate) (PICM), or from about 30 to about 100 wt.%, Or from about 50 to about 100 wt.%, or from about 75 to about 100 wt.%. In other non-limiting embodiments of the invention, the cycloaliphatic isocyanate may consist essentially of the trans-trans isomer 1,1'-methylene bis (4-isocyanatocyclohexane) (also known as 4,4'-methylene bis (cyclohexyl isocyanate)), for example, at least from at least about 80% by weight of the trans-trans isomer of 1,1'-methylene-bis (4-isocyanatocyclohexane), or from at least about 90% by weight of the trans-trans isomer of 1,1'-methylene-bis (4-isocyanatocyclohexane), or at least about 95% by weight of the trans-trans isomer of 1,1'-methylene bis (4-isocyanato iklogeksana), and in other nonlimiting embodiments, it contains approximately 100 wt.% trans-trans isomer of 1,1'-methylene-bis (4-izotsianatotsiklogeksana).

Non-limiting examples of suitable polyisocyanates for use in the present invention are polyisocyanates and polyisothiocyanates having basic bridges such as urethane bridges (-NH-C (O) -O-), thiourethane bridges (-NH-C (O) -S-), thiocarbamate bridges (-NH-C (S) -O-), dithiourethane bridges (-NH-C (S) -S-), polyamide bridges and combinations thereof.

Other non-limiting examples of suitable polyisocyanates include ethylenically unsaturated polyisocyanates and polyisothiocyanates; alicyclic polyisocyanates and polyisothiocyanates; aromatic polyisocyanates and polyisothiocyanates, wherein the isocyanate groups are not directly bonded to the aromatic ring, for example, α, α'-xylylene diisocyanate; aromatic polyisocyanates and polyisothiocyanates, wherein the isocyanate groups are bonded directly to the aromatic ring, for example, benzenediisocyanate; aliphatic polyisocyanates and polyisothiocyanates containing sulfide bridges; aromatic polyisocyanates and polyisothiocyanates containing sulfide or disulfide bridges; aromatic polyisocyanates and bridges; polyisocyanates and polyisothiocyanates containing sulfonic polyisothiocyanates of the sulfonic ester type, for example 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester; aromatic polyisocyanates and sulfonamide-type polyisothiocyanates; sulfur-containing heterocyclic polyisocyanates and polyisothiocyanates, for example thiophene-2,5-diisocyanate; halogenated, alkylated, alkoxylated, nitrated, carbodiimide modified, urea modified and biuret modified isocyanate derivatives and dimerized and trimerized isocyanate products.

Non-limiting examples of suitable ethylenically unsaturated polyisocyanates are butenediisocyanate and 1,3-butadiene-1,4-diisocyanate. Non-limiting examples of suitable alicyclic polyisocyanates are isophorondiisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl) -2,2-isomethane, bis (isocyanocyclohexyl) -2,2-isomethane, 3- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo [2.2.1] heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2.2.1] heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl ) -5-isocyanatomethylbicyclo [2.2.1] heptane, 2-isocyanatomethane -2- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2.2.1] heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane, 2-isocyanatomethyl -2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) bicyclo [2.2.1] heptane and 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane.

Non-limiting examples of suitable aromatic polyisocyanates where the isocyanate groups are not directly linked to the aromatic ring are α, α'-xyldiisocyanate, bis (isocyanatoethyl) benzene, α, α, α ', α'-tetramethylxylene diisocyanate, 1,3-bis (1- isocyanato-1-methyl-ethyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylenetriisocyanate and 2,5-di (isocyanatomethyl) furan.

Nonlimiting examples of suitable aromatic polyisocyanates having isocyanate groups bonded directly to the aromatic ring, are phenylene, etilfenilendiizotsianat, izopropilfenilendiizotsianat, dimetilfenilendiizotsianat, dietilfenilendiizotsianat, diizopropilfenilendiizotsianat, trimetilbenzoltriizotsianat, benzoldiizotsianat, benzoltriizotsianat, naphthalene, metilnaftalindiizotsianat, biphenyl, ortotoluidindiizotsianat, ortotolilidindiizotsianat, ortotolilendiizotsiana 4,4'-diphenylmethanediisocyanate, bis (3-methyl-4-isocyanatophenyl) methane, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymer 4,4'-diphenylmethanediisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 4-methyl diphenylmethane-3,5,2 ', 4', 6'-pentaisocyanate, diphenyl ether diisocyanate, bis (isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl ether) -1,3 -propylene glycol, benzophenone diisocyanate, carbazoldiisocyanate, ethyl carbazoldiisocyanate and dichlorocarbazoldiisocyanate.

In some non-limiting embodiments, sulfur-containing isocyanates of the following general formula (I) may be used:

where R ₁₀ and R ₁₁ each independently represents C ₁ -C ₃ alkyl.

Non-limiting examples of suitable aliphatic polyisocyanates containing sulphide bridges are thioethyl diisocyanate, thiodipropyl diisocyanate, dithiodihexyl diisocyanate, dimethyl sulfonodiisocyanate, dithiodimethyldiisocyanate, dithiodiethyldiisocyanate di-dithiodisyloisodiocyanated dihydroisodiocyanated. Non-limiting examples of suitable aromatic polyisocyanates containing sulfide or disulfide bridges include, but are not limited to, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanato-dibenzylthioether bis (4-isocyanatomethylbenzene) sulfide, diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3 ' -dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxyphenyl disulfide- 4,4'-diisocyanate and 4,4'-dimethoxyphenyl disulfide-3,3'-diisocyanate.

Non-limiting examples of suitable aromatic polyisocyanates containing sulfonic bridges are diphenyl sulfon-4,4'-diisocyanate, diphenyl sulfon-3,3'-diisocyanate, benzidine sulfon-4,4'-diisocyanate, diphenylmethanesulfon-4,4'-diisocyanate, 4-methyl -2,4'-diisocyanate, 4,4'-dimethoxyphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyl diphenylsulfon-3,3'-diisocyanate; and 4,4'-dichlorodiphenylsulfon-3,3'-diisocyanate.

Non-limiting examples of sulfonamide-type aromatic polyisocyanates are 4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonylethylenediamine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonylethylenediamine-3,3-di-3-di-3-diamine methyl 3-isocyanatobenzenesulfonylanilide-4-ethyl-3'-isocyanate.

Non-limiting examples of suitable isothiocyanates are cyclohexanediisothiocyanates; aromatic isothiocyanates, where the isothiocyanate group (s) is not connected (s) directly to the aromatic ring; aromatic isothiocyanates, where the isothiocyanate group (s) is connected (s) directly to the aromatic ring; heterocyclic isothiocyanates; carbonyl polyisothiocyanates; aliphatic polyisothiocyanates containing sulfide bridges, as well as mixtures thereof.

Other non-limiting examples of suitable isothiocyanates are aromatic polyisothiocyanates, wherein the isothiocyanate groups are bonded directly to the aromatic ring, such as phenylenediisothiocyanate; heterocyclic polyisothiocyanates, such as 2,4,6-triisothiocyanato-1,3,5-triazine and thiophene-2,5-diisothiocyanate; carbonyl polyisothiocyanates; aliphatic polyisothiocyanates containing sulfide bridges, such as thiobis (3-isothiocyanatopropane); aromatic polyisothiocyanates containing sulfur atoms in addition to atoms of isothiocyanate groups; halogenated, alkylated, alkoxylated, nitrated, carbodiimide modified, urea modified and biuret modified derivatives of such polyisothiocyanates and dimerized and trimerized products of such isothiocyanates.

Non-limiting examples of suitable aliphatic polyisothiocyanates are 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane and 1,6-diisothiocyanatohexane. Non-limiting examples of aromatic polyisothiocyanates containing isothiocyanate groups linked directly to the aromatic ring are 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-cyanato 4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylene bis (4-isothiocyanatobenzene), 1,1'-methylene bis (4-isothiocyanato-2-methylbenzene), 1,1 ' -methylene bis (4-isothiocyanato-3-methylbenzene), 1,1 '- (1,2-ethanediyl) bis (4-isothiocyanatobenzene), 4,4'-diisothiocyanato-benzophenone, 4,4'-diisothiocyan to-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4,4'-diisothiocyanate and diphenylamine-4,4'-diisothiocyanate.

Non-limiting examples of suitable carbonyl isothiocyanates are hexanedioyldiisothiocyanate, nonanedioyldiisocyanate, carbonic acid diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate and (2,2'-bipyridinothiocyanate-4,4'-4. Non-limiting examples of suitable aromatic polyisothiocyanates containing sulfur atoms in addition to the atoms of the isothiocyanate groups are 1-isothiocyanato-4 - [(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isobenziobis (4-isobenoliobis (4-isobenoliobis) -isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato-1 - [(4-isothiocyanatophenyl) sulfonyl] -2-methoxybenzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4-3-4-isothiocyanatobenzene -isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocia nat.

Other non-limiting examples of isocyanates having isocyanate and isothiocyanate groups are materials containing aliphatic, alicyclic, aromatic or heterocyclic groups, which optionally may contain sulfur atoms in addition to the atoms of the isothiocyanate groups. Non-limiting examples of such materials are 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isocyanato-carbonyl isothiocyanate, 1-isocyanato-4-isothiocyanato-4-iso-cyano-4-iso-cyano -3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanato-4'-isothiocyanatodiphenyl sulfide and 2-isocyanato-2'-isothiocyanato-diethyl disulfide.

In certain non-limiting embodiments, the isocyanate comprises at least one triisocyanate or at least one triisocyanate trimer. Non-limiting examples of such isocyanates are aromatic triisocyanates such as tris (4-isocyanatophenyl) methane (DESMODUR R), 1,3,5-tris (3-isocyanato-4-methylphenyl) -2,3,6-trioxohexahydro-1,3 5-triazine (DESMODUR IL); aromatic diisocyanate adducts such as the adduct of 2,4-tolylene diisocyanate (TDI, 2,4-diisocyanatotoluene) and trimethylolpropane (DESMODUR L); and aliphatic triisocyanates such as N-isocyanatohexylaminocarbonyl-N, N'-bis (isocyanatohexyl) urea (DESMODUR N), 2,4,6-trioxo-1,3,5-tris (6-isocyanatohexyl) hexahydro-1,3 5-triazine (DESMODUR N3390), 2,4,6-trioxo-1,3,5-tris (5-isocyanato-1,3,3-trimethylcyclohexylmethyl) hexahydro-1,3,5-triazine (DESMODUR Z4379) and 4- (isocyanatomethyl) -1,8-octanediisocyanate. The DESMODUR products above are commercially available from Bayer Corp. Hexanediisocyanate biuret, polymeric methanediisocyanate and polymeric isophorondiisocyanate, trimers of hexamethylene diisocyanate, isophorondiisocyanate and tetramethylxylene diisocyanate can also be used.

In some non-limiting embodiments, the polyisocyanate used as a precursor for preparing the polyurethane polyol prepolymer is a cycloaliphatic compound, such as a binuclear compound bonded by an isopropylidene group or an alkylene group of 1-3 carbon atoms.

The reaction components for the preparation of Group A polyurethane also include from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups. As discussed above, a branched polyol can increase free volume within a polymer matrix to provide space for movement or rotation of molecules upon impact.

As used herein, the term “polyol” includes compounds, monomers, oligomers and polymers containing at least two hydroxyl groups (eg, diols) or at least three hydroxyl groups (eg, triols), higher functional polyols and their mixtures. Suitable polyols are capable of forming a covalent bond with reactive groups, such as an isocyanate functional group.

Non-limiting examples of suitable polyols are aliphatic, cycloaliphatic, aromatic, heterocyclic, oligomeric and polymeric polyols and mixtures thereof. In some embodiments, for example, in the case of transparent products or windows exposed to sunlight, aliphatic or cycloaliphatic polyols can be used.

The number of carbon atoms in the polyol described above for Group A may range from 4 to 18, or from 4 to 12, or from 4 to 10, or from 4 to 8, or from 4 to 6 carbon atoms. In some non-limiting embodiments of the invention, one or more carbon atoms in the polyol may be substituted with one or more heteroatoms, such as N, S, or O.

As discussed above, a branched polyol that can be used as a reaction product to produce Group A polyurethane contains from 4 to 18 carbon atoms and at least 3 hydroxyl groups. Non-limiting examples of trifunctional, tetrafunctional, and higher polyols for use as branched polyols are branched chain alkanopolols such as glycerol, tetramethyl methane, trimethyl ethane (e.g. 1,1,1-trimethyl ethane), trimethylol propane (TMP) (e.g. 1,1 , 1-trimethylolpropane), erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, their alkoxylated derivatives (described below), as well as mixtures thereof.

In some non-limiting embodiments of the invention, the polyol may be a cycloalkane polyol, for example trimethylene bis (1,3,5-cyclohexanetriol).

In some non-limiting embodiments of the invention, the polyol may be an aromatic polyol, for example trimethylene bis (1,3,5-benzene triol).

Other non-limiting examples of suitable polyols include the polyols mentioned above, which may be alkoxylated derivatives, for example ethoxylated, propoxylated and butoxylated derivatives. In alternative non-limiting embodiments, the following polyols can be alkoxylated with 1-10 alkoxy groups: glycerol, trimethylol ethane, trimethylol propane, benzene triol, cyclohexanetriol, erythritol, pentaerythritol, sorbitol, mannitol, sorbitan, dipentaerythritol and tripentaerythritol. In alternative non-limiting embodiments, the alkoxylated, ethoxylated and propoxylated polyols and mixtures thereof can be used alone or in combination with non-alkoxylated, non-ethoxylated and non-propoxylated polyols containing at least three hydroxyl groups, and mixtures thereof. The number of alkoxy groups can be from 1 to 10, or from 2 to 8, or any suitable number between 1 and 10. In a non-limiting embodiment, the alkoxy group can be an ethoxy group, and the number of ethoxy groups can be from 1 to 5 units. In another non-limiting embodiment of the invention, the polyol may be trimethylolpropane containing up to 2 ethoxy groups. Non-limiting examples of suitable alkoxylated polyols are ethoxylated trimethylol propane, propoxylated trimethylol propane, ethoxylated trimethylol ethane, and mixtures thereof.

Mixtures of any of the above polyols may be used.

In some embodiments of the invention, the polyurethanes of the present invention can be thermoplastics, for example polyurethanes having a molecular weight for crosslinking of at least about 6000 g / mol.

In some non-limiting embodiments of the invention, a branched polyol containing from 4 to 18 carbon atoms may have a number average molecular weight of from about 100 to about 500 g / mol. In some non-limiting embodiments of the invention, the polyol may have a number average molecular weight of less than about 450 g / mol. In other non-limiting embodiments of the invention, the polyol may have a number average molecular weight of less than about 200 g / mol.

The reaction components for the preparation of Group A polyurethane also contain from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms, or from about 2 to about 14 carbon atoms, or from 2 to 10 carbon atoms, or 2 to 6 carbon atoms. In some non-limiting embodiments, one or more carbon atoms in the diol may be substituted with one or more heteroatoms, such as N, S, or O.

Non-limiting examples of suitable diols include linear alkanediols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,2-ethanediol; propanediols such as 1,2-propanediol and 1,3-propanediol; butanediols such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol; pentanediols such as 1,5-pentanediol, 1,3-pentanediol and 2,4-pentanediol; hexanediols such as 1,6-hexanediol and 2,5-hexanediol; heptanediols such as 2,4-heptanediol; octanediols such as 1,8-octanediol; nonanediols such as 1,9-nonanediol; decanediols such as 1,10-decanediol; dodecandiols, such as 1,12-dodecandiol; octadecandiols, such as 1,18-octadecandiol; sorbitol, mannitol and mixtures thereof. In some non-limiting embodiments, the diol is propanediol, such as 1,2-propanediol and 1,3-propanediol, or butanediol, such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. In some non-limiting embodiments of the invention, one or more carbon atoms in the polyol may be substituted with one or more heteroatoms, such as N, S or O; for example, sulfonated polyols such as dithiooctane-bisdiol, thiodiethanol, such as 2,2-thiodiethanol or 3,6-dithia-1,2-octanediol.

Other non-limiting examples of suitable diols include diols represented by the following formula:

where R is a C ₀ -C ₁₈ bivalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic or oligomeric saturated alkylene radical, or mixtures thereof; A C ₂ -C ₁₈ divalent organic radical containing at least one element selected from the group consisting of a sulfur, oxygen and silicon atom in addition to carbon and hydrogen atoms; A C ₅ -C ₁₈ divalent saturated cycloalkylene radical or a C ₅ -C ₁₈ divalent saturated heterocycloalkylene radical; and R ′ and R ″ may be present or absent, and if present, each independently represents a C ₁ -C ₁₈ divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric or oligomeric saturated alkylene radical, or mixtures thereof .

Other non-limiting examples of suitable diols are branched alkanediols such as propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 2-methylbutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl -1,3-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, dibutyl-1,3-propanediol, polyalkylene glycols such as polyethylene glycol, and mixtures thereof.

In some non-limiting embodiments of the invention, the diol may be cycloalkanediol, such as cyclopentanediol, 1,4-cyclohexanediol; cyclohexane dimethanols (CHDM) such as 1,4-cyclohexane dimethanol, cyclododecandiol, 4,4'-isopropylidene biscyclohexanol, hydroxypropyl cyclohexanol, cyclohexane diethanol, 1,2-bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxyethyl) cyclohexane, 4 -isopropylidenebiscyclohexanol, bis (4-hydroxycyclohexanol) methane and mixtures thereof.

In some non-limiting embodiments, the implementation of the diol may be an aromatic diol, such as dihydroxybenzene, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol and dihydroxytoluene; bisphenols such as 4,4'-isopropylidene diphenol, 4,4'-hydroxybisphenol, 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis (4-hydroxyphenyl) methane, 4,4 '- (1, 2-ethenediyl) bisphenol and 4,4'-sulfonylbisphenol; halogenated bisphenols such as 4,4'-isopropylidenebis (2,6-dibromophenol), 4,4'-isopropylidenebis (2,6-dichlorophenol) and 4,4'-isopropylidenebis (2,3,5,6-tetrachlorophenol) ; alkoxylated bisphenols which may have, for example, ethoxy, propoxy, α-butoxy and β-butoxy groups; and biscyclohexanols, which can be obtained by hydrogenation of the corresponding bisphenols, such as 4,4'-isopropylidenebiscyclohexanol, 4,4'-hydroxybiscyclohexanol and 4,4'-thiobiscyclohexanol and bis (4-hydroxycyclohexanol) methane, 1 mole alkylation product 2.2 bis (4-hydroxyphenyl) propane (i.e., bisphenol-A) with 2 moles of propylene oxide; hydroxyalkyl terephthalates, such as meta- or para-bis (2-hydroxyethyl) terephthalate, bis (hydroxyethyl) hydroquinone, and mixtures thereof.

In some non-limiting embodiments of the invention, the diol may be a heterocyclic diol, for example dihydroxypiperidine, such as 1,4-bis (hydroxyethyl) piperazine.

In some non-limiting embodiments of the invention, the diol may be an amide or alkanamide (such as ethanediamide (oxamide)), for example N, N'-bis (2-hydroxyethyl) oxamide.

In some non-limiting embodiments of the invention, the diol may be a diol of propionate, for example 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.

In some non-limiting embodiments of the invention, the diol may be a hydantoin diol, such as bishydroxypropylhydantoin.

In some non-limiting embodiments of the invention, the diol may be a phthalate diol, such as meta- or para-bis (2-hydroxyethyl) terephthalate.

In some non-limiting embodiments of the invention, the diol may be a hydroquinone diol, such as dihydroxyethylhydroquinone.

In some non-limiting embodiments of the invention, the diol may be an isocyanurate diol, such as dihydroxyethyl isocyanurate.

In some non-limiting embodiments, the implementation of the diol for use in the present invention may be an SH-containing material, such as polythiols having at least three thiol groups and from 4 to 18 carbon atoms. Non-limiting examples of suitable polythiols may include, but are not limited to, aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, heterocyclic polythiols, polymer polythiols, oligomeric polythiols and mixtures thereof. Material containing sulfur and containing an active hydrogen atom can have bridges, including, but not limited to, ether bridges (-O-), sulfide bridges (-S-), polysulfide bridges (-S _x -, where x is at least 2 or from 2 to 4) and combinations of such bridges. The definitions of “thiol”, “thiol group”, “mercapto” or “mercapto group” used in this case refer to the SH group, which is capable of forming a thiourethane bridge (i.e., -NH-C (O) -S-) with an isocyanate a group or a dithiourethane bridge (i.e., -NH-C (S) -S-) with an isothiocyanate group.

In some non-limiting embodiments, the implementation of the polyurethane components essentially do not include SH-containing materials, that is, contain less than about 5 wt.% SH-containing material, in other non-limiting embodiments, they contain less than about 2 wt.% SH-containing materials, and in other non-limiting embodiments, SH-containing materials are absent.

In some non-limiting embodiments of the invention, a diol containing from 4 to 18 carbon atoms may have a number average molecular weight of from about 200 to about 10,000 g / mol, or less than about 500 g / mol, or less than about 200 g / mol.

Mixtures of any of the above diols may be used.

In some non-limiting embodiments of the invention, the reaction components for preparing a Group A polyurethane may further include one or more unbranched triols and / or one or more unbranched, more highly functional polyols.

Non-limiting examples of suitable unbranched triols and unbranched, more highly functional polyols include aliphatic, cycloaliphatic, aromatic, heterocyclic, oligomeric and polymeric polyols, as well as mixtures thereof.

In some non-limiting embodiments of the invention, the polyol may be a cycloalkane polyol, such as cyclohexanetriol (e.g., 1,3,5-cyclohexanetriol).

In some non-limiting embodiments of the invention, the polyol may be an aromatic polyol, such as benzene triol (e.g., 1,2,3-benzene triol, 1,2,4-benzene triol and 1,3,5-benzene triol) and phenolphthalein.

In some non-limiting embodiments of the invention, the polyol may be an isocyanurate polyol, such as tris (hydroxyethyl) isocyanurate.

In some non-limiting embodiments of the invention, the reaction components for preparing Group A polyurethane may further include one or more branched or unbranched polyols (diols, triols and / or more highly functional polyols) containing more than 18 carbon atoms.

Non-limiting examples of suitable polyols containing more than 18 carbon atoms are linear or branched aliphatic polyols, cycloaliphatic polyols, aromatic polyols, heterocyclic polyols, oligomeric polyols, polymer polyols and mixtures thereof.

Non-limiting examples of suitable linear or branched aliphatic polyols containing more than 18 carbon atoms are 1,18-eicosanediol and 1,24-tetracosanediol.

Other non-limiting examples of suitable polyols containing more than 18 carbon atoms are polyols represented by the following formula:

where R is a C ₀ -C ₃₀ bivalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic or oligomeric saturated alkylene radical, or mixtures thereof; A C ₂ -C ₃₀ divalent organic radical containing at least one element selected from the group consisting of a sulfur, oxygen and silicon atom, in addition to carbon and hydrogen atoms; A C ₅ -C ₃₀ divalent saturated cycloalkylene radical or a C ₅ -C ₃₀ divalent saturated heterocycloalkylene radical; and R ′ and R ″ may be present or absent, and if present, each independently represents a C ₁ -C ₃₀ divalent linear or branched, aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric or oligomeric saturated alkylene radical, or mixtures thereof .

Non-limiting examples of suitable cycloaliphatic polyols containing more than 18 carbon atoms are biscyclohexanols containing more than 18 carbon atoms, which can be obtained by hydrogenation of the corresponding bisphenols.

Non-limiting examples of suitable aromatic polyols containing more than 18 carbon atoms are bisphenols, alkoxylated bisphenols, such as alkoxylated 4,4'-isopropylidene diphenol, which may contain from 3 to 70 alkoxy groups.

Other non-limiting examples of suitable oligomeric and polymeric polyols having more than 18 carbon atoms include higher polyalkylene glycols such as polyethylene glycols having number average molecular weights in the range of from about 200 to about 2000 g / mol, as well as mixtures thereof.

In some non-limiting embodiments, the polyol for use in the present invention may be an SH-containing material, such as polythiols containing at least two thiol groups or at least three thiol groups and at least 18 atoms carbon. Non-limiting examples of suitable polythiols may include, but are not limited to, aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, heterocyclic polythiols, polymer polythiols, oligomeric polythiols, and mixtures thereof. Material containing sulfur and containing an active hydrogen atom can have bridges, including, but not limited to, ether bridges (-O-), sulfide bridges (-S-), polysulfide bridges (-S _x -, where x is at least 2 or from 2 to 4) and combinations of such bridges. The definitions of “thiol”, “thiol group”, “mercapto” or “mercapto group” used in this case refer to the SH group, which is capable of forming a thiourethane bridge (i.e., -NH-C (O) -S-) with an isocyanate a group or a dithiourethane bridge (i.e., -NH-C (S) -S-) with an isothiocyanate group.

In some non-limiting embodiments, the implementation of the polyurethane components essentially do not include SH-containing material, that is, contain less than about 5 wt.% SH-containing material, in other non-limiting embodiments, they contain less than about 2 wt.% SH-containing materials, and in other non-limiting embodiments, SH-containing materials are absent.

In some non-limiting embodiments, a polyol containing at least 18 carbon atoms may have a number average molecular weight of from about 200 to about 5000 g / mol, or from about 200 to about 4000 g / mol, or at least about 200 g / mol, or at least about 400 g / mol, or at least about 1000 g / mol, or at least about 2000 g / mol. In some non-limiting embodiments of the invention, the polyol may have a number average molecular weight of less than about 5000 g / mol, or less than about 4000 g / mol, or less than about 3000 g / mol, or less than about 2000 g / mol, or less than about 1000 g / mol, or less than about 500 g / mol.

Mixtures of any of the above polyols may be used. For example, the polyol may include trimethylolpropane, and the diol may include butanediol and / or pentanediol.

As discussed above, the amount of branched polyol used to produce Group A polyurethane is from about 0.1 to about 0.9 equivalents. In some non-limiting embodiments of the invention, the amount of branched polyol used to make the polyurethane is from about 0.3 to about 0.9 equivalents. In other non-limiting embodiments of the invention, the amount of branched polyol used to make the polyurethane is about 0.3 equivalent.

As discussed above, the amount of diol used to prepare Group A polyurethane is from about 0.1 to about 0.9 equivalents. In some non-limiting embodiments of the invention, the amount of diol used to make the polyurethane is from about 0.3 to about 0.9 equivalents. In other non-limiting embodiments of the invention, the amount of diol used to make the polyurethane is about 0.3 equivalent.

In some non-limiting embodiments of Group A polyurethanes, the reaction components contain from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, and from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms per 1 equivalent of at least one polyisocyanate, wherein said components are substantially free of polyester polyol and polyether polyol, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

In some embodiments, the polyurethane comprises a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); from about 0.3 to about 0.5 equivalent of trimethylolpropane; and from about 0.3 to about 0.7 equivalent of butanediol or pentanediol, or about 0.7 equivalent of butanediol or pentanediol; where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In another embodiment, the present invention provides Group A polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); about 0.3 equivalents of trimethylolpropane; and about 0.7 equivalents of 1,10-dodecanediol; where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In another embodiment, the present invention provides Group A polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); about 0.3 equivalent of trimethylolpropane; and about 0.7 equivalent of 1,5-pentanediol; where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In another embodiment, the present invention provides Group A polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 0.3 equivalent of trimethylolpropane; approximately 0.7 equivalent of 1,4-butanediol; where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

In another embodiment, the present invention provides Group A polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 0.4 equivalent trimethylolpropane; approximately 0.6 equivalent of 1,18-octadecandiol; where the reaction components are maintained at a temperature of at least about 100 ° C. for at least about 10 minutes.

Group A polyurethanes can exhibit good ballistic resistance, such as penetration resistance, penetration resistance, or cracking due to impact from a projectile, such as a bullet, or a shot that is fired from a gun, gun, rifle, AK-47 or other shooting devices or explosives. In some embodiments, Group A polyurethanes 0.75 '' (1.9 cm) thick or more will stop or reflect: a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411.5 m / s) from a distance of 20 feet; a 0.40 caliber bullet fired at an initial speed of 987 ft / s (300.8 m / s) from a distance of 20 feet (6.1 m); and / or a 12-caliber gun shell fired at an initial speed of 1290 ft / s (393.2 m / s) from a distance of 20 feet (6.1 m).

Group B

In some non-limiting embodiments, the present invention provides Group B polyurethanes containing a reaction product of components comprising: (a) an isocyanate-functional urethane prepolymer containing a reaction product of components comprising: (i) approximately 1 equivalent of at least one polyisocyanate and ( ii) from about 0.1 to about 0.5 equivalents of at least one diol containing from 2 to 18 carbon atoms, (b) from about 0.05 to about 0.9 equivalents, at least m D, one polyol comprising from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (c) up to about 0.45 equivalent of at least one diol containing from 2 to 18 carbon atoms, wherein said components are substantially free of polyester polyol and polyether polyol.

Non-limiting examples and amounts of suitable polyisocyanates, diols and polyols for use in reaction products to produce Group B polyurethanes are discussed in detail above when considering Group A. Methods for producing Group B polyurethanes are discussed in more detail below.

Group C

In some non-limiting embodiments, the present invention provides Group C polyurethanes containing a reaction product of components comprising: at least one polyisocyanate selected from the group consisting of triisomers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups, wherein said components are substantially free of polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention provides Group C polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 1.1 equivalents of butanediol; and approximately 0.1 equivalents of the isophorondiisocyanate trimer.

Non-limiting examples of suitable trimers of polyisocyanate, branched polyisocyanates and aliphatic polyols (including, but not limited to linear, branched or cycloaliphatic polyols) for use as reaction products for the production of Group C polyurethanes are discussed in detail above when considering Group A. Can be used amounts of trimer (s) of polyisocyanate and / or branched (s) polyisocyanate (s) similar to those described above for Group A polyisocyanate. In addition, d I Group C preparing polyurethanes can be used a mixture of trimer (s), polyisocyanate and / or branched (s), polyisocyanate (s) with straight or other netrimerizovannymi polyisocyanates described above.

In some non-limiting embodiments of a Group C polyurethane, the reaction components contain from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, per 1 the equivalent of at least one polyisocyanate, and in other non-limiting embodiments, from about 0.3 to about 0.9 equivalents of at least one aliphatic polyol containing from 2 to 18 carbon atoms, where Said components are substantially free of polyester polyol and polyether polyol.

As discussed above, in some non-limiting embodiments of Group A, Group B and Group C, the reaction product of the components is substantially free of polyester polyol and polyether polyol. Used in this case, the expression "essentially does not contain polyester polyol and polyether polyol" means that the reaction product of the components contains less than about 10 wt.% Polyester and / or polyether polyol, or less than about 5 wt.% Polyester and / or polyether polyol, or less than about 2 wt.% polyester polyol and / or polyether polyol, or do not contain polyester and / or polyether polyol.

Non-limiting examples of such polyester polyols are glycol polyesters, polycaprolactone polyols, polycarbonate polyols and mixtures thereof. Polyester glycols may include the esterification products of one or more dicarboxylic acids containing from four to ten carbon atoms, for example, but without limitation, adipic, succinic or sebacic acids, with one or more low molecular weight glycols containing from two to ten carbon atoms, such as, but not limited to, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and 1,10-decanediol. The esterification procedures for the production of polyester polyols are described, for example, in D.M. Young, F. Hostettler et al. “Polyesters from Lactone”, Union Carbide F-40, p. 147.

Non-limiting examples of polycaprolactone polyols are polyols obtained by condensation of caprolactone in the presence of a bifunctional material with an active hydrogen atom, such as water or low molecular weight glycols, for example ethylene glycol and propylene glycol. Non-limiting examples of suitable polycaprolactone polyols can be commercially available materials, designated as the CAPA series from Solvay Chemical of Houston, Texas, such as CAPA 2047A and CAPA 2077A, and the TONE series from Dow Chemical of Midland, Michigan, such as TONE 0201, 0210, 0230 and 0241. In some non-limiting embodiments, the polycaprolactone polyol has a molecular weight in the range of from about 500 to about 2000 g / mol or from about 500 to about 1000 g / mol.

Non-limiting examples of polycarbonate polyols are aliphatic polycarbonate diols, for example, diols based on alkylene glycols, glycol ethers, alicyclic glycols, or mixtures thereof. In some embodiments, alkylene groups for producing polycarbonate polyol may contain from 5 to 10 carbon atoms and may be linear, cycloalkylene, or combinations thereof. Non-limiting examples of such alkylene groups are hexylene, octylene, decylene, cyclohexylene and cyclohexyl dimethylene. Suitable polycarbonate polyols can be prepared in non-limiting examples by reacting a hydroxy-terminated alkylene glycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or a diaryl carbonate, such as diphenyl or dinaphthyl carbonate, or by the reaction ending in hydroxy alkylenediol group with phosgene or bischloroformate by methods known to those skilled in the art. Non-limiting examples of such polycarbonate polyols are polycarbonate polyols, commercially available as Ravecarb ^™ 107 from Enichem SpA (Polimeri Europa) (Italy), and number average molecular weight polyhexylene carbonate diols, such as KM10-1733 polycarbonate diol derived from hexanediol, a commercial product. Examples of other suitable polycarbonate polyols that are commercially available are KM10-1122, KM10-1667 (obtained from a mixture of 50/50 wt.% Cyclohexanedimethanol and hexanediol) (commercially available from Stahl USA Inc. of Peabody, Massachusetts) and DESMOPHEN 2020E (commercially available from Bayer Corp.).

Polycarbonate polyol can be obtained by reacting a diol, such as described above, and a dialkyl carbonate, such as described in US patent No. 4160853. Polycarbonate polyol can include polyhexamethylene carbonate, such as HO- (CH ₂ ) ₆ - [OC (O) -O- (CH ₂ ) ₆ ] _n -OH, where n takes integer values from 4 to 24, or from 4 to 10, or from 5 to 7.

Non-limiting examples of polyether polyols are poly (oxyalkylene) polyols or polyalkoxylated polyols. Poly (oxyalkylene) polyols can be prepared according to known methods. In a non-limiting embodiment, the poly (oxyalkylene) polyol can be prepared by condensing an alkylene oxide or mixture of alkylene oxides using an acid-catalyzed or base addition with a polyatomic initiator or a mixture of polyatomic initiators such as ethylene glycol, propylene glycol, glycerol and sorbitol. Compatible blends of polyether polyols can also be used. Used in this case, the definition of "compatible" means that two or more materials can be mutually dissolved in each other so that essentially one phase is formed. Non-limiting examples of alkylene oxides may include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides such as styrene oxide, mixtures of ethylene oxide and propylene oxide. In some non-limiting embodiments, polyoxyalkylene polyols can be prepared with mixtures of alkylene oxide using statistical or stepwise hydroxyalkylation. Non-limiting examples of such poly (oxyalkylene) polyols are polyoxyethylene polyols, such as polyethylene glycol, and polyoxypropylene polyols, such as polypropylene glycol.

Other simple polyether polyols are block polymers, such as block polymers having ethylene oxide-propylene oxide and / or ethylene oxide-butylene oxide blocks. In some non-limiting embodiments of the invention, polyether polyols include a block copolymer of the following formula:

HO- (CHR ₁ CHR ₂ -O) _a - (CHR ₃ CHR ₄ -O) _b - (CHR ₅ CHR ₆ -O) _c -H,

where R ₁ -R ₆ each independently may represent a hydrogen atom or methyl; and a, b and c each independently can be selected from integers from 0 to 300, where a, b and c are chosen so that the number average molecular weight of the polyol is less than about 32,000 g / mol or less than about 10,000 g / mol at determination using GPC (GPC). In other non-limiting embodiments, a, b, and c may each independently be an integer from 1 to 300. In other non-limiting embodiments, R ₁ , R ₂ , R _5, and R ₆ may represent a hydrogen atom, and R ₃ and R ₄ each independently selected from a hydrogen atom and methyl, provided that R ₃ and R ₄ are different from each other. In other non-limiting embodiments, R ₃ and R ₄ may represent a hydrogen atom, and R ₁ and R ₂ each independently can be selected from a hydrogen atom and methyl, provided that R ₁ and R ₂ are different from each other, and R ₅ and R _6, each independently can be selected from a hydrogen atom and methyl, provided that R ₅ and R ₆ are different from each other.

In some non-limiting embodiments, the implementation of polyalkoxysilane polyols can be represented by the following General formula:

Formula (I ')

where m and n each can take positive integer values, the sum of m and n being from 5 to 70; R ₁ and R ₂ each represents a hydrogen atom, methyl or ethyl; and A represents a divalent linking group, such as linear or branched alkylene, which may contain from 1 to 8 carbon atoms, phenylene and C ₁ -C ₉ -alkyl-substituted phenylene. The values of m and n can, in combination with the selected divalent linking group, determine the molecular weight of the polyol. Polyalkoxylated polyols can be prepared by methods that are well known in the art. In non-limiting embodiments, a polyol, such as 4,4'-isopropylidene diphenol, can be reacted with an oxirane-containing material, such as ethylene oxide, propylene oxide or butylene oxide, to form a material commonly referred to as an ethoxylated, propoxylated or butoxylated polyol having hydroxyl functionality. Non-limiting examples of polyols suitable for use in the preparation of polyalkoxylated polyols can be polyols, which are described in US patent No. 6187444 B1, column 10, lines 1-20, which is incorporated into the description by reference.

In some non-limiting embodiments, the polyether polyol may be PLURONIC ethylene oxide / propylene oxide block copolymers, such as PLURONIC R and PLURONIC L62D, and / or TETRONIC ethylene oxide and propylene oxide tetra-functional block copolymers, such as TETRONIC R, which are commercially available from BASFAS ., Parsippany, New Jersey.

Used in this case, the expression "simple polyether polyols" may also include poly (oxytetramethylene) diols obtained by polymerization of tetrahydrofuran in the presence of catalysts, Lewis acids, such as, but not limited to, boron trifluoride, tin (IV) chloride and sulfonyl chloride.

Group D

In some non-limiting embodiments, the present invention provides Group D polyurethanes comprising a reaction product of components comprising: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or combinations thereof. Brominated or phosphonated polyols can give polyurethane with increased fire resistance. The fire resistance of the polyurethanes of the present invention can be determined by a simple flame to determine if the polymer is self-extinguishing or burns more slowly than the polymer in the absence of a brominated or phosphonated polyol, or in accordance with the Underwritter's Laboratory Test UL-94.

In other non-limiting embodiments, the present invention provides Group D polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); from about 0.3 to about 0.5 equivalent of trimethylolpropane; from about 0.2 to about 0.5 equivalent of bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) sulfone; from about 0.2 to about 0.5 equivalent of 1,4-cyclohexanedimethanol; and from about 0.2 to about 0.5 equivalent of 3,6-dithia-1,2-octanediol.

Non-limiting examples of suitable polyisocyanates and branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups for use as reaction products to produce Group D polyurethanes are discussed in detail above when considering Group A.

Non-limiting examples of suitable polyols containing one or more bromine atoms, one or more phosphorus atoms, or a combination thereof, are 4,4'-isopropylidene bis (2,6-dibromophenol), isopropylidene bis [2- (2,6-dibromophenoxy ) ethanol], bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) sulfone, heptakis (dipropylene glycol) triphosphite, tris (dipropylene glycol) phosphate, diethyl N, N-bis (2-hydroxyethyl) aminoethanol phosphonate and mixtures thereof . Non-limiting examples of suitable phosphonated polyols are polyols of the formula HO-YO [POOR-OYO] [POOR-OY] -OH, where each R is independently selected from an alkylene group having 1-10 repeating units, for example, CH ₂ to (CH ₂ ) ₁₀ and each Y is independently selected from an alkylene group having from 1 to 6 repeating units, for example, from CH ₂ to (CH ₂ ) ₆ .

The amount of brominated polyols and / or phosphonated polyols used to produce Group D polyurethane may be from about 0.1 to about 0.9 equivalents, or from about 0.3 to about 0.9 equivalents, or about 0.3 equivalents.

In some non-limiting embodiments of the invention, the reaction components may also include one or more polyether polyols and / or polyester polyols described above. If present, the amount of polyether polyols and / or polyester polyols used to prepare Group D polyurethane may be from about 0.1 to about 0.9 equivalent, or from about 0.3 to about 0.9 equivalent, or about 0.3 equivalent.

Groups A-D

In some non-limiting embodiments of the implementation of the polyurethanes of groups AD, the reaction products may additionally contain one or more of the following components: polyurethane polyols, (meth) acrylamides, hydroxy (meth) acrylamides, polyvinyl alcohols, polymers containing (meth) acrylates with hydroxyl functionality, polymers containing allyl alcohols, polyetheramides and mixtures thereof. In some embodiments, acrylamide polymerization can produce interpenetrating polymer networks having high transparency, good toughness, and high Young's modulus.

Non-limiting examples of suitable polyurethane polyols are the reaction products of an excess of polyisocyanate and a branched or linear polyol. The equivalent ratio of polyisocyanate to polyol may range from about 1.0: 0.05 to about 1.0: 0.3, or is about 1.0: 0.7. The amount of polyurethane polyols used can range from about 1 to about 90 wt.%, From about 5 to about 70 wt.%, Or from about 20 to about 50 wt.% Based on the total weight of the components.

Non-limiting examples of suitable acrylamides are acrylamide, methacrylamide and dimethyl acrylamide. Acrylamide can be added together with all other components of the reaction, or it can be dissolved in a diol and then mixed with other components of the reaction. The amount of acrylamide used can range from about 5 to about 70 wt.%, From about 10 to about 50 wt.%, Or from about 10 to about 30 wt.% Based on the total weight of the components.

Non-limiting examples of suitable polyvinyl alcohols include polyvinyl alcohol. The amount of polyvinyl alcohol used can range from about 5 to about 90 wt.%, From about 10 to about 70 wt.%, Or from about 10 to about 40 wt.% Based on the total weight of the components.

Non-limiting examples of suitable polymers containing (meth) acrylates with hydroxyl functionality are hydroxypropyl acrylate; hydroxyethyl acrylate; hydroxypropyl methacrylate; hydroxyethyl methacrylate and copolymers containing the hydroxyl functionality of (meth) acrylates with acrylamides, cyanoethyl (meth) acrylates, methyl methacrylates, methacrylates, ethacrylates, propyl acrylates and vinyl pyrrolidone. The amount of hydroxyl functionality (meth) acrylates used can range from about 10 to about 90 wt.%, From about 10 to about 70 wt.%, Or from about 10 to about 30 wt.% Based on the total weight of the components.

Non-limiting examples of suitable polymers containing allyl alcohols are diethylene glycolbis (allyl carbonate), allyloxytrimethylsilane and diallyl carbonate. The amount of allyl alcohols used can range from about 5 to about 70 wt.%, From about 10 to about 50 wt.%, Or from about 10 to about 30 wt.%.

Non-limiting examples of suitable polyetheramides are ether polymers obtained by reacting bis-oxamidodiols, such as N, N'-bis (omega-hydroxyalkylene) oxamide, with a dicarboxylic acid or diester such as diethyl oxalate, diethyl succinate, diethyl superate or dimethyl terephthalate. The amount of polyetheramides used can range from about 10 to about 80 wt.%, From about 20 to about 60 wt.%, Or from about 30 to about 50 wt.% Based on the total weight of the components.

In some non-limiting embodiments of Group A-C polyurethanes, the reaction products may further comprise one or more amine curing agents. The amine curing agent, if present, can act as a catalyst in the polymerization reaction, can be incorporated into the obtained polymerizate, and can form poly (urethane ureas). The amount of amine curing agent used can range from about 0.05 to about 0.9 equivalents, from about 0.1 to about 0.7 equivalents, or from about 0.3 to about 0.5 equivalents.

Non-limiting examples of such amine curing agents are aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, and mixtures thereof. In some non-limiting embodiments of the invention, the amine curing agent may have at least two functional groups selected from a primary amine (-NH ₂ ), a secondary amine (-NH-), and combinations thereof. In some non-limiting embodiments, the amine curing agent may have at least two primary amine groups. In some non-limiting embodiments, all amino groups are primary groups.

Examples of such amine curing agents are compounds having the following formula:

where R ₁ and R ₂ each independently selected from methyl, ethyl, propyl and isopropyl groups, and R ₃ selected from a hydrogen atom and chlorine; for example, the following compounds manufactured by Lonza Ltd. (Basel, Switzerland): LONZACURE ^® M-DIPA, in which R ₁ = C ₃ H ₇ ; R ₂ = C ₃ H ₇ ; R ₃ = H; LONZACURE ^® M-DMA, in which R ₁ = CH ₃ ; R ₂ = CH ₃ ; R ₃ = H; LONZACURE ^® M-MEA, in which R ₁ = CH ₃ ; R ₂ = C ₂ H ₅ ; R ₃ = H; LONZACURE ^® M-DEA, in which R ₁ = C ₂ H ₅ ; R ₂ = C ₂ H ₅ ; R ₃ = H; LONZACURE ^® M-MIPA, in which R ₁ = CH ₃ ; R ₂ = C ₃ H ₇ ; R ₃ = H; and LONZACURE ^® M-CDEA, wherein R ₁ = C ₂ H _5; R ₂ = C ₂ H ₅ ; R ₃ = Cl; each of which is commercially available from Air Products and Chemicals, Inc., Allentown, PA.

Such amine curing agents can comprise a diamine curing agent such as 4,4'-methylene-bis (3-chloro-2,6-diethylaniline) (LONZACURE ^® M-CDEA); 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene and mixtures thereof (collectively "diethyltoluene diamine" or "DETDA", which is commercially available from Albemarle Corporation under the trade name ETHACURE 100; dimethylthiotoluene diamine (DMTDA) (commercially available as ETHACURE 300); a color-stabilized version of ETHACURE 100 (i.e. a formulation containing an additive to reduce yellow staining), which is available under the name ETHACURE 100S; 4,4'-methylene bis (2-chloroaniline ) (commercially available from Kingyorker Chemicals under the name MOSA.) DETDA may be liquid at room temperature with a viscosity of 156 centipoise (cps) at 25 ° C. DETDA can be isomeric, with the amount of 2,4-isomer is from 75 to 81%, whereas the 2,6 isomer can be from 18 to 24%.

Other non-limiting examples of amine curing agents are ethylene amines, such as ethylene diamine (EDA), diethylene triamine (DETA), triethylenetetraamine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexane (RENA), piperazine, morpholine, substituted dipyridine, diphenediamine, diphenediamine DEDA) and 2-amino-1-ethylpiperazine. In some non-limiting embodiments, the implementation of the amine curing agent may be selected from one or more isomers of C ₁ -C ₃ dialkyltoluene-diamine, such as 3,5-dimethyl-2,4-toluene diamine, 3,5-dimethyl-2,6- toluene diamine, 3,5-diethyl-2,4-toluene diamine, 3,5-diethyl-2,6-toluene diamine, 3,5-diisopropyl-2,4-toluene diamine, 3,5-diisopropyl-2,6-toluene diamine and mixtures thereof. In some non-limiting embodiments, the implementation of the amine curing agent may be methylenedianiline or trimethylene glycol di (para-aminobenzoate).

Other non-limiting examples of amine curing agents include compounds having the following general structures (XIII-XV):

Other non-limiting examples of amine curing agents include one or more methylene bis (anilines) represented by general formulas XVI-XX, one or more aniline sulfides represented by general formulas XXI-XXV, and / or one or more bianilins represented by general formulas XXVI- XXIX:

where R ₃ and R _{4 are} each independently C ₁ -C ₃ alkyl and R _{5 is} selected from a hydrogen atom and a halogen such as chlorine or bromine. The diamine represented by the general formula XV can be described as 4,4'-methylene bis (dialkylaniline). Suitable non-limiting examples of diamines which may be represented by general formula XV include, but are not limited to, 4,4'-methylene bis (2,6-dimethylaniline), 4,4'-methylene bis (2,6-diethylaniline ), 4,4'-methylene bis (2-ethyl-6-methylaniline), 4,4'-methylene bis (2,6-diisopropylaniline), 4,4'-methylene bis (2-isopropyl-6 -methylaniline) and 4,4'-methylene-bis (2,6-diethyl-3-chloroaniline).

The amine curing agent may include compounds represented by the following general structure (XXX):

where R ₂₀ , R ₂₁ , R ₂₂ and R _{23 are} each independently selected from H, C ₁ -C ₃ alkyl, CH ₃ -S - and halogen such as chlorine or bromine. An amine curing agent represented by general formula XXX may include diethyltoluene diamine (DETDA), where R ₂₃ is methyl, R ₂₀ and R _{21 are} each ethyl and R ₂₂ is a hydrogen atom. In addition, the amine curing agent may include 4,4'-methylenedianiline.

In an embodiment of the invention where it is desired to produce a poly (urethane urea) having a low coloration, the amine curing agent may be selected so that it has a relatively low coloration and / or can be produced and / or stored in such a way as to prevent staining of the amine ( for example, its yellowing).

In some non-limiting embodiments of Group AD polyurethanes, the reaction products may substantially be free of an amine curing agent. Used in this case, the expression "essentially do not contain amine curing agent" means that the reaction product of the components contains less than about 10 wt.% Amine curing agent, or less than about 5 wt.% Amine curing agent, or less than about 2 wt. .% amine curing agent, or in other non-limiting embodiments, no amine curing agent.

Group E

In some non-limiting embodiments, the present invention provides Group E polyurethanes comprising a reaction product of components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol; where these components are essentially free of simple polyether polyol and an amine curing agent, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, polycarbonate diols and a diol containing from 2 to 18 carbon atoms, for use as reaction products for the preparation of Group E polyurethanes are discussed more detailed above when considering Group A.

In some non-limiting embodiments, the amount of branched polyol used to form Group E polyurethane may range from about 0.3 to about 0.98 equivalent, or from about 0.5 to about 0.98 equivalent, or about 0.3 equivalent, or from about 0.9 to about 0.98 equivalents.

In some non-limiting embodiments, the amount of polycarbonate diol used to form Group E polyurethane may range from about 0.01 to about 0.1 equivalent, or from about 0.05 to about 0.1 equivalent, or about 0.1 equivalent.

In another embodiment, the present invention provides Group E polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 0.3 equivalent of trimethylolpropane; approximately 0.55 equivalents of 1,5-pentanediol and approximately 0.15 equivalents of KM10-1733 polycarbonate diol derived from hexanediol available from Stahl, where the reaction components are held at a temperature of at least about 100 ° C, at least for about 10 minutes

In another embodiment, the present invention provides Group E polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 0.3 equivalent of trimethylolpropane; about 0.5 equivalent of 1,5-pentanediol and about 0.2 equivalent of KM10-1733 polycarbonate diol derived from hexanediol available from Stahl, where the reaction components are maintained at a temperature of at least about 100 ° C, at least for about 10 minutes.

Group E polyurethanes can exhibit good ballistic stability.

Group E polyurethanes are substantially free of polyether polyol and an amine curing agent, the types and amounts of polyether polyol and amine curing agent described above with regard to Groups A-D.

In some non-limiting embodiments of Group E polyurethanes, the reaction products may further comprise one or more of the following components: polyurethane polyols, acrylamides, polyvinyl alcohols, polymers containing (meth) acrylates with hydroxyl functionality, polymers containing allyl alcohols, polyesters and mixtures thereof, as described, and in the amounts presented above when considering AD Groups.

Group F

In some non-limiting embodiments, the present invention provides Group F polyurethanes containing a reaction product of components comprising: (a) about 1 equivalent of at least one polyisocyanate; (b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; (c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol; and (d) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 atoms carbon; where these components are essentially free of polyether polyol and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes. A diol containing from 2 to 18 carbon atoms is chemically different from a polycarbonate diol, for example a diol has at least one other atom or atom arrangement in comparison with polycarbonate diol.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, polycarbonate diols and diols containing from 2 to 18 carbon atoms, for use as reaction products for the preparation of Group F polyurethanes are described in detail above when considering Group A.

In some non-limiting embodiments, the amount of branched polyol used to prepare Group F polyurethane may range from about 0.3 to about 0.98 equivalent, or from about 0.5 to about 0.98 equivalent, or from about 0, 9 to about 0.98 equivalent.

In some non-limiting embodiments, the amount of polycarbonate diol used to prepare Group F polyurethane may be in the range of from about 0.01 to about 0.1 equivalent, or from about 0.05 to about 0.1 equivalent, or can be about 0.1 equivalent .

In some non-limiting embodiments, the amount of diol used to prepare Group F polyurethane may be in the range of from about 0.01 to about 0.1 equivalent, or from about 0.05 to about 0.1 equivalent, or can be about 0.1 equivalent .

Group F polyurethanes are substantially free of polyether polyol, with the types and amounts of polyether polyol described above with regard to Groups A-D.

In some non-limiting embodiments of Group F polyurethanes, the reaction products may further comprise one or more of the following components: polyurethane polyols, acrylamides, polyvinyl alcohols, polymers containing (meth) acrylates with hydroxyl functionality, polymers containing allyl alcohols, polyesters and mixtures thereof, as described, and in the amounts presented above when considering AD Groups.

In some non-limiting embodiments of Group F polyurethanes, the reaction products may additionally contain one or more amine curing agents, as discussed above with respect to Group E. In other non-limiting embodiments, the reaction products for producing Group F polyurethanes may substantially or not contain an amine curing agent as discussed above when considering Groups A-D.

Group G

In some non-limiting embodiments, the present invention provides Group G polyurethanes comprising a reaction product of components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; from about 0.01 to about 0.3 equivalents of at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol, and mixtures thereof; and from about 0.1 to about 0.7 equivalents of at least one aliphatic diol; where these components are essentially free of simple polyether polyol and an amine curing agent, and where the reaction components are held at a temperature of at least about 100 ° C for at least about 10 minutes.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, polyester polyols, polycarolactones polyols and aliphatic diols for use as reaction products for the production of Group G polyurethanes are described in detail above when considering Groups A. The aliphatic diol is chemically different from the polyester polyol and polycaprolactone polyol, for example, the diol has at least one other atom or another arrangement atoms as compared with a polyether polyol and a polycaprolactone polyol.

In some non-limiting embodiments, the amount of branched polyol used to prepare Group G polyurethane may range from about 0.3 to about 0.9 equivalents, or from about 0.3 to about 0.7 equivalents, or from about 0, 4 to about 0.6 equivalent or approximately 0.7 equivalent.

In some non-limiting embodiments, the amount of polyester and / or polycaprolactone polyol used to prepare Group GF polyurethane may range from about 0.01 to about 0.1 equivalent, or from about 0.05 to about 0.1 equivalent, or may be approximately 0.1 equivalent.

In some non-limiting embodiments, the amount of aliphatic diol used to prepare Group G polyurethane may be in the range of about 0.1 to about 0.6 equivalent, or from about 0.1 to about 0.5 equivalent, or can be about 0.5 equivalent.

Group G polyurethanes are substantially free or free of polyether polyol and / or amine curing agent, the types and amounts of polyether polyol and amine curing agent described above with regard to Groups AD.

In some non-limiting embodiments of Group G polyurethanes, the reaction products may additionally contain one or more of the following components: polyurethane polyols, acrylamides, polyvinyl alcohols, polymers containing (meth) acrylates with hydroxyl functionality, polymers containing allyl alcohols, polyesters and mixtures thereof, as described, and in the amounts presented above when considering AD Groups.

In other non-limiting embodiments, the present invention provides Group G polyurethanes containing a reaction product of components comprising: about 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); approximately 0.3 equivalent of trimethylolpropane; about 0.5 equivalent of decanediol and about 0.2 equivalent of polycaprolactone polyol, such as polycaprolactone polyol Dow TONE 0210, having a number average molecular weight of about 1000 g / mol, where the reaction components are held at a temperature of at least about 100 ° C, at least , for about 10 minutes.

In other non-limiting embodiments, the present invention provides Group G polyurethanes derived from a prepolymer that is a reaction product of components comprising: (1) approximately 0.4 equivalents of 4,4'-methylene bis (cyclohexyl isocyanate) (such as DESMODUR W) ; (2) approximately 0.3 equivalents of polycaprolactone diol (such as polycaprolactone diols CAPA 2047 and CAPA 2077A derived from hexanediol); (3) approximately 0.05 equivalent of trimethylolpropane. The prepolymer is reacted with at least one aliphatic diol containing from 2 to 18 carbon atoms, as described above, for example with butanediol or pentanediol.

Group H

In some non-limiting embodiments, the present invention provides Group H polyurethanes containing a reaction product of components comprising: (a) a prepolymer that is a reaction product of components comprising: (1) at least one polyisocyanate; (2) at least one polycaprolactone polyol; and (3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof; and (b) at least one diol containing from 2 to 18 carbon atoms.

Non-limiting examples of suitable polyisocyanates, polycaprolactone polyols, polyalkylene polyols, polyether polyols and diols containing from 2 to 18 carbon atoms for use as a reaction product for the production of Group H polyurethanes are discussed in more detail above when considering Group A. Non-limiting examples of suitable polyalkylene polyols are polyethylene glycols, polypropylene glycols mixtures thereof. The polyalkylene glycol may have a number average molecular weight in the range of from about 200 to about 1000 g / mol or from about 200 to about 4000 g / mol.

The diol is chemically different from polyalkylene polyol and polyether polyol, for example, the diol has at least one other atom or atom arrangement in comparison with polyalkylene polyol and polyether polyol.

In some non-limiting embodiments, the amount of branched polycaprolactone polyol used to prepare Group H polyurethane may range from about 0.05 to about 0.8 equivalent, or from about 0.1 to about 0.6 equivalent, or from about 0, 1 to about 0.4 equivalent or approximately 0.3 equivalent.

In some non-limiting embodiments, the amount of polyalkylene polyol and / or polyether polyol used to prepare Group H polyurethane may be in the range of from about 0.1 to about 0.9 equivalents, or from about 0.2 to about 0.6 equivalents, or about 0.4 equivalent.

In some non-limiting embodiments, the amount of diol used to prepare Group H polyurethane may range from about 0.1 to about 0.9 equivalents, or from about 0.3 to about 0.8 equivalents, or is about 0.7 equivalents.

Group H polyurethanes are prepared by reaction of reaction product components, including: (1) at least one polyisocyanate; (2) at least one polycaprolactone polyol; and (3) at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol, and mixtures thereof; with the formation of prepolymer. The prepolymer is then reacted with at least one diol containing from 2 to 18 carbon atoms and any other optional reaction components described below.

In some non-limiting embodiments of Group H polyurethanes, the reaction products may additionally contain one or more of the following components: branched polyols containing at least three hydroxyl groups, polyurethane polyols, acrylamides, polyvinyl alcohols, polymers containing (meth) acrylates with hydroxyl functionality, polymers containing allyl alcohols, polyesters and mixtures thereof, as described, and in the amounts presented above when considering Groups AD.

In some non-limiting embodiments of Group H polyurethanes, the reaction products may additionally contain one or more amine curing agents, which are discussed above with respect to Group E. In other non-limiting embodiments, the reaction products for the preparation of Group H polyurethanes may essentially contain no or no amine curing agent as discussed above when considering Groups A-D.

In other non-limiting embodiments, the present invention provides Group H polyurethanes containing a reaction product of components comprising: (a) a prepolymer that is a reaction product of components comprising: (1) an aliphatic or cycloaliphatic diisocyanate; (2) polycaprolactone diol; (3) polyethylene glycol; and (4) polyoxyethylene and polyoxypropylene copolymer; and (b) at least one diol containing from 2 to 18 carbon atoms.

In other non-limiting embodiments, the present invention provides Group H polyurethanes derived from a prepolymer that is a reaction product of components comprising: (1) approximately 0.4 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate) (such as DESMODUR W) ; (2) approximately 0.003 equivalents of polycaprolactone diol (such as polycaprolactone diol 2077A derived from hexanediol); (3) approximately 0.025 equivalents of polyethylene glycol (such as PLURACOL E400NF); (4) approximately 0.029 equivalents of polyoxyethylene and polyoxypropylene copolymers (such as ethylene oxide / propylene oxide block copolymer PLURONIC L62D); (5) approximately 0.05 equivalents of trimethylolpropane and additives such as a catalyst (e.g. dibutyltin dilaurate), an antioxidant (such as IRGANOX 1010 and IRGANOX MD 1024), and UV stabilizers such as CYASORB UV 5411 and TINUVIN 328 (each described below).

An isocyanate-terminated prepolymer is reacted with at least one diol containing from 2 to 18 carbon atoms, such as 1,4-butanediol and / or 1,4-cyclohexanedimethanol, in an equivalent ratio of 1,4-butanediol to 1,4-cyclohexanedimethanol approximately 0.75: 0.25. The equivalent ratio of prepolymer to diol is approximately 1: 1.

Groups AH

As for Groups AH, the polyurethanes of the present invention can be polymerized using various techniques. In some non-limiting embodiments described in more detail below, the polyisocyanate and the polyol can be reacted with each other in the same process vessel to form a polyurethane. Sulfur-containing polyurethanes of the present invention can be obtained by mixing isocyanate and / or isothiocyanate and polyol and / or polythiol.

In other non-limiting embodiments of the invention, polyurethanes can be prepared by reacting polyisocyanate (s) and polyol (s) to form a polyurethane prepolymer and then introducing diol (s) and optionally a catalyst and other optional reaction components.

In other non-limiting embodiments, such as Group B, a polyurethane can be prepared by reacting the polyisocyanate (s) and the diol (s) to form an urethane prepolymer with isocyanate functionality and then introducing the diol (s), polyols and optionally a catalyst and other optional reaction components. In some embodiments of the invention, an isocyanate functional urethane prepolymer, a polyol, and a second portion of the diol from the reaction components are held at a temperature of at least about 100 ° C. for at least about 10 minutes or at least about 110 ° C for at least about 10 or 20 minutes.

Regardless of being obtained in a single-step process or in a multi-stage process using a prepolymer in some non-limiting embodiments of the invention, each of the above-mentioned ingredients can be degassed (degassed) prior to the reaction. In some non-limiting embodiments of the invention, the prepolymer can be degassed, the bifunctional material can be degassed, and then the two materials can be mixed.

In the “single operation” method or in bulk polymerization, all ingredients, that is, isocyanate, polyol and diol, are mixed simultaneously. This method, as a rule, is satisfactory when all active hydrogen atoms react at approximately the same speed, for example, when all contain hydroxyl groups in the form of single reactive sites. The urethane reaction can be carried out under anhydrous conditions with dry reagents, for example, in a nitrogen atmosphere at atmospheric pressure and at a temperature in the range from about 75 ° C to about 140 ° C. If polycarbonate polyols or any compounds with hydroxyl functionality are used, they are usually dried before the reaction, usually to a moisture content in the range of from about 0.01 to about 0.05%.

To obtain the desired statistics and, as a rule, a transparent polymer, a diol, for example anhydrous 1,4-butanediol (containing a maximum of 0.04% water), can be added to the polyol in a nitrogen atmosphere to eliminate moisture, and the temperature is kept high enough so that phase separation is absent, and get a homogeneous mixture. A polyisocyanate, for example 4,4'-methylene bis (cyclohexyl isocyanate), can be added quickly and the mixture can be maintained at a temperature of at least about 75 ° C, or at least about 85 ° C, or, at least about 90 ° C, or at least about 95 ° C for at least about 10 minutes or at least about 20 minutes. In some embodiments, the mixture is maintained at a temperature of at least about 100 ° C, or at least about 105 ° C, or at least about 110 ° C for at least about 10 minutes, or at least about 20 minutes so that phase separation is absent and the mixture remains homogeneous. The mixture may be aged at a pressure in the range of from about 2 to about 6 mmHg (from about 266.6 to about 800 Pa) or at about 266.6 Pa for a period of time from about 10 minutes to about 24 hours, or approximately 10 minutes to approximately 4 hours.

In some non-limiting embodiments, the mixtures are intensively mixed at a temperature of at least about 75 ° C, or at least about 85 ° C, or at least about 90 ° C, or at least about 95 ° C, or at least about 100 ° C, or at least about 105 ° C, or at least about 110 ° C, and degassed for a period of time of at least about 3 minutes, and during this time the pressure is reduced from atmospheric pressure to approximately 3 m Hg The pressure reduction facilitates the removal of dissolved gases such as nitrogen and carbon dioxide, and then the ingredients can be reacted at a temperature in the range of from about 100 to about 140 ° C or from about 110 to about 140 ° C in the presence of a catalyst, and the reaction is continued until essentially no isocyanate groups remain, in some embodiments, for at least about 6 hours. In the absence of a catalyst, the reaction can be carried out for at least about 24 hours, for example, in a nitrogen atmosphere.

In some non-limiting embodiments, where a window can be formed, a polymerizable mixture, which optionally can be degassed, can be introduced into the melt, and the melt can be heated (i.e., a thermal curing cycle) using a number of conventional techniques known in the art technicians. The thermal cure cycle may vary depending on reactivity and molar ratio of reactants. In a non-limiting embodiment, the curing cycle may include heating a mixture of prepolymer and diol and optionally diol and dithiol or heating a mixture of polyisocyanate, polyol and / or polythiol and diol and / or diol / dithiol from room temperature to a temperature of about 200 ° C for a period of time from about 0.5 to about 72 hours; or from about 80 ° C to about 150 ° C for a period of time from about 5 to about 48 hours.

In other non-limiting embodiments described in more detail below, the isocyanate and the polyol can react with each other to form a polyurethane prepolymer, and the prepolymer can be reacted with an additional large amount of the same or different polyol (s) and / or diol (s) to form polyurethane or sulfur-containing polyurethane. Using the prepolymer method, the prepolymer and diol (s) can be heated so as to reduce the viscosity of the prepolymer to about 200 cP or at most up to several thousand centipoises to facilitate mixing. As with bulk polymerization, the reaction must be carried out under anhydrous conditions with dry reagents.

The polyurethane prepolymer may have a number average molecular weight (Mn) of less than about 50,000 g / mol, or less than about 20,000 g / mol, or less than about 10,000 g / mol, or less than about 5,000 g / mol, or at least , about 1000 g / mol, or at least about 2000 g / mol, including any interval between them.

When polyurethane-forming components, such as polyols and isocyanates, are mixed to produce polyurethanes, the relative amounts of ingredients are generally expressed as the ratio of the number of available reactive isocyanate groups to the number of available reactive hydroxyl groups, i.e. the equivalent ratio of NCO: OH . For example, an NCO: OH ratio of 1.0: 1.0 is obtained when one equivalent of the NCO of the fed form of the isocyanate component is reacted with a mass of one equivalent of OH of the fed form of the organic polyol component. The polyurethanes of the present invention may have an equivalent NCO: OH ratio in the range of from about 0.9: 1.0 to about 1.1: 1.0, or the ratio is about 1.0: 1.0.

In some non-limiting embodiments, when the isocyanate and the polyol are reacted to form a prepolymer, the isocyanate is present in excess, for example, the amount of isocyanate and the amount of polyol in the isocyanate prepolymer can be selected so that the equivalent ratio (NCO) :( OH) can be in a range of from about 1.0: 0.05 to about 1.0: 0.7.

In some non-limiting embodiments, the amount of isocyanate and the amount of polyol used to produce the isocyanate-terminated polyurethane prepolymer or the isocyanate-terminated polyurethane prepolymer can be selected so that the equivalent ratio (NCO) :( SH + OH) can be at least about 1.0: 1.0, or at least about 2.0: 1.0, or at least about 2.5: 1.0, or less than about 4.5: 1.0, or less than about 5.5: 1.0; or the amount of isothiocyanate and the amount of polyol used to produce the sulfur-containing polyurethane prepolymer with an end isothiocyanate group can be selected so that the equivalent ratio (NCS) :( SH + OH) can be at least about 1.0: 1.0 or at least about 2.0: 1.0, or at least about 2.5: 1.0, or less than about 4.5: 1.0, or less than about 5.5 : 1.0; or the amount of a combination of isothiocyanate and isocyanate and the amount of polyol used to produce the sulfur-containing polyurethane prepolymer with an end isothiocyanate / isocyanate group can be selected so that the equivalent ratio (NCS + NCO) :( SH + OH) can be at least approximately 1.0: 1.0, or at least about 2.0: 1.0, or at least about 2.5: 1.0, or less than about 4.5: 1.0, or less than about 5.5: 1.0.

The ratio and proportions of the diol and polyol can affect the viscosity of the prepolymer. The viscosity of such prepolymers can be improved, for example, if they are intended for use with coating compositions, for example with compositions for spray coating processes. The solids content of such prepolymers, however, can also be important, since with a higher solids content, the desired coating properties, such as weather resistance, scratch resistance, etc. can be achieved. In conventional coatings, coating compositions with a higher content solids typically require higher amounts of solvent to dilute the coating in order to reduce the viscosity for the respective spray coating processes. The use of such solvents, however, can adversely affect the surface of the substrate, especially when the surface of the substrate is a polymeric material. In the present invention, the viscosity of the prepolymer can be appropriately adjusted to obtain a material with lower viscosity levels at a higher solids content, resulting in an effective coating without the need for extremely large amounts of solvents that can adversely affect the surface of the substrate.

In some non-limiting embodiments of the present invention that use an optional amine curing agent, an amount of an isocyanate-terminated polyurethane prepolymer or an isocyanate-terminated polyurethane prepolymer and an amount of an amine curing agent used to produce a sulfur-containing polyurethane can be selected so that an equivalent ratio (NH + SH + OH) :( NCO) could be in the range from about 0.80: 1.0 to about 1.1: 1.0, or from approx. reliably 0.85: 1.0 to about 1.0: 1.0, or from about 0.90: 1.0 to about 1.0: 1.0, or from about 0.90: 1.0 to about 0.95: 1.0, or from about 0.95: 1.0 to about 1.0: 1.0.

In some non-limiting embodiments of the present invention, the amount of an isothiocyanate or isothiocyanate / isocyanate terminal sulfur-containing polyurethane prepolymer and the amount of amine curing agent used to produce the sulfur-containing polyurethane can be selected so that the equivalent ratio (NH + SH + OH) :( NCO + NCS) ) could be in the range from about 0.80: 1.0 to about 1.1: 1.0, or from about 0.85: 1.0 to about 1.0: 1.0, or from about 0.90 : 1.0 to about 1.0: 1.0, or about about 0.90: 1.0 to about 0.95: 1.0 or about 0.95: 1.0 to about 1.0: 1.0.

It is believed that the unusual energy absorption characteristics and transparency of the polyurethanes of the present invention may depend not only on the ingredients and proportions of the urethane, but may also depend on the preparation method. More specifically, it is believed that the presence of polyurethane ordered block segments can adversely affect the transparency characteristics of the polyurethane and energy absorption, and therefore, it is believed that statistical segments within the polymer can give optimal results. Therefore, whether urethane contains statistical or ordered block segments depends on the specific reagents and their relative reactivity, as well as on the reaction conditions. In general, the polyisocyanate will be more reactive with a low molecular weight diol or polyol, for example 1,4-butanediol, than with a polymer polyol, and therefore, in some non-limiting embodiments of the invention, it is desirable to inhibit preferred reactions between a low molecular weight diol or polyol and a polyisocyanate, for example by rapidly adding a polyisocyanate to a well-mixed mixture of a low molecular weight diol or polyol and a polymer polyol with vigorous stirring, for example, at a temperature of at least at least about 75 ° C when the catalyst is not used, and then by keeping at the reaction temperature at least about 100 ° C or about 110 ° C after the exothermic reaction has taken place. When using a catalyst, the initial mixing temperature may be lower, for example, approximately 60 ° C, so that the exotherm does not raise the temperature of the mixture well above the desired reaction temperature. Although polyurethanes are thermally stable, nevertheless, reaction temperatures can reach about 200 ° C and be below about 60 ° C and in some non-limiting embodiments range from about 75 to about 130 ° C when using a catalyst or in the range from about 80 to approximately 100 ° C. When the catalyst is not used, in some non-limiting embodiments of the invention, the reaction temperature may range from about 130 to about 150 ° C.

It is also desirable to quickly reach reaction temperatures after obtaining a homogeneous mixture when the catalyst is not used, so that the polymer does not become cloudy due to phase separation. For example, some mixtures without a catalyst may become cloudy in less than half an hour at a temperature of less than 80 ° C. Therefore, it may be desirable to use a catalyst or to introduce reagents, for example, using a high-speed intensive mixing shift head to quickly reach a reaction temperature above about 100 ° C, or about 110 ° C, or about 130 ° C so that the polymer does not become cloudy. Suitable catalysts may be selected from catalysts known in the art. In some non-limiting embodiments of the invention, degassing can be performed before or after addition of the catalyst.

In some non-limiting embodiments, a urethane forming catalyst may be used in the present invention to accelerate the reaction of polyurethane forming materials. Suitable urethane-forming catalysts are those that can be useful for the formation of urethane by the reaction of NCO- and OH-containing materials and which have a slight tendency to accelerate side reactions leading to the formation of allophonate and isocyanate. Non-limiting examples of suitable catalysts are selected from Lewis bases, Lewis acids, and inclusion catalysts as described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1992, Volume A21, pp. 673-674.

In some non-limiting embodiments, the implementation of the catalyst may be a tin salt of an organic acid, such as tin octanoate and butyl stannic acid. Other non-limiting examples of suitable catalysts include tertiary amine catalysts, tertiary ammonium salts, tin catalysts, phosphines, or mixtures thereof. In some non-limiting embodiments, the catalyst may be dimethylcyclohexylamine, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, dibutyltin diacetate, dibutyltin diamethylate, dimethyltin diacetate, dimethyltin diacetate, benzocarbonate, diacidobenzoate, mixtures. The amount of catalyst used may vary depending on the amount of components, for example, from about 10 to about 600 ppm.

In alternative non-limiting embodiments of the invention, various additives may be included in compositions containing the polyurethane (s) of the present invention. Such additives include light stabilizers, thermal stabilizers, antioxidants, dyes, flame retardants, ultraviolet absorbers, light stabilizers, such as light stabilizers based on hindered amines, mold release agents, static (non-photochemical) dyes, fluorescent agents, pigments, surface active substances, plasticizing additives, such as, but not limited to, alkoxylated phenol benzoates and poly (alkylene glycol) dibenzoates, as well as mixtures thereof. Non-limiting examples of yellowing additives are 3-methyl-2-butenol, organic pyrocarbonates and triphenylphosphite (Reg. CAS No. 101-02-0). Examples of useful antioxidants are IRGANOX 1010, IRGANOX 1076, and IRGANOX MD 1024, each of which is commercially available from Ciba Specialty Chemicals, Tarrytown, New York. Examples of suitable UV absorbers are CYASORB UV 5411, TINUVIN 130 and TINUVIN 328, which are commercially available from Ciba Specialty Chemicals, as well as SANDOVAR 3206, which is commercially available from Clariant Corp., Charlotte, North Carolina. An example of useful hindered amine light stabilizers is SANDOVAR 3056, which is commercially available from Clariant Corp., Charlotte, North Carolina. An example of useful surfactants is BYK 306, which is commercially available from BYK Chemie, Wesel, Germany.

These additives may be present in amounts such that the additive produces less than about 30 wt.%, Or less than about 15 wt.%, Or less than about 5 wt.%, Or less than about 3 wt.% Based on the total weight polymer. In some non-limiting embodiments, the aforementioned optional additives may be premixed with polyisocyanate (s) or with a prepolymer with isocyanate functionality. In other non-limiting embodiments of the invention, optional additives may be premixed with the polyol (s) or urethane prepolymer.

In some non-limiting embodiments, the present invention provides methods for producing Group A polyurethanes, which include the step of simultaneously reacting components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms, where the components are substantially free of polyester polyol and polyether polyol.

In other non-limiting embodiments, the present invention provides methods for producing Group A polyurethanes, which include the steps of: reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and the interaction of the polyurethane prepolymer with at least one diol containing from 2 to 18 carbon atoms, with the formation of polyurethane.

In other non-limiting embodiments, the present invention provides methods for producing Group B polyurethanes, which include the steps of:

(a) interactions (i) about 1 equivalent of at least one polyisocyanate; and (ii) from about 0.1 to about 0.5 equivalent of at least one diol containing from 2 to 18 carbon atoms to form urethane prepolymer with isocyanate functionality;

(b) the interaction of the urethane prepolymer with isocyanate functionality and from about 0.05 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, and up to about 0.45 equivalents of at least one diol containing from 2 to 18 carbon atoms, where the components of the reaction product are substantially free of polyester polyol and polyether polyol.

In some non-limiting embodiments, the present invention provides methods for producing Group C polyurethanes, which include the step of simultaneously reacting components, comprising: at least one trimer of a polyisocyanate or a branched polyisocyanate, wherein the polyisocyanate has at least three isocyanate functional groups; and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least two hydroxyl groups; where the components of the reaction product are substantially free of polyester polyol and polyether polyol.

In some non-limiting embodiments, the present invention provides methods for producing Group D polyurethanes, which comprise the step of simultaneously reacting components including: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or combinations thereof.

In other non-limiting embodiments, the present invention provides methods for producing Group D polyurethanes, which comprise the steps of: reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and the interaction of the polyurethane prepolymer with at least one polyol containing one or more bromine atoms, one or more phosphorus atoms, or a combination thereof and, with the formation of polyurethane. In some non-limiting embodiments, from about 0.1 to about 0.15 equivalents of the branched polyol reacts with about 1 equivalents of the polyisocyanate in step (a), and step (b) further includes reacting the polyurethane prepolymer with the polyol and from about 0.15 to about 0 , 9 equivalents of branched polyol to form polyurethane.

In some non-limiting embodiments, the present invention provides methods for producing Group E polyurethanes, which comprise the step of simultaneously reacting components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol, where the components of the reaction product are substantially free of polyether polyol and an amine curing agent.

In other non-limiting embodiments, the present invention provides methods for producing Group E polyurethanes, which comprise the steps of: reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and the interaction of the polyurethane prepolymer with at least one polycarbonate diol to form a polyurethane.

In some non-limiting embodiments, the present invention provides methods for producing Group F polyurethanes, which comprise a step of simultaneously reacting components comprising: (a) about 1 equivalent of at least one polyisocyanate; (b) from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; (c) from about 0.01 to about 0.3 equivalents of at least one polycarbonate diol; and (d) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 atoms carbon, where the components of the reaction product are substantially free of polyether polyol.

In other non-limiting embodiments, the present invention provides methods for producing Group F polyurethanes, which comprise the steps of: (a) reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least , 3 hydroxyl groups, with the formation of a polyurethane prepolymer and (b) the interaction of the polyurethane prepolymer with at least one polycarbonate diol and with at least one diol containing from 2 to 18 carbon atoms, with images polyurethane, where the components of the reaction product are substantially free of polyether polyol.

In some non-limiting embodiments, the present invention provides methods for producing Group G polyurethanes, which comprise the step of simultaneously reacting components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.3 to about 1 equivalent of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; and from about 0.01 to about 0.3 equivalents of at least one polyol selected from the group consisting of polyester polyol, polycaprolactone polyol, and mixtures thereof; and from about 0.1 to about 0.7 equivalents of at least one aliphatic diol; where the components of the reaction product are substantially free of polyether polyol and an amine curing agent.

In other non-limiting embodiments, the present invention provides methods for producing Group G polyurethanes, which comprise the steps of: reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of a polyurethane prepolymer and the interaction of the polyurethane prepolymer with at least one polyol selected from the group comprising polyester polyol, polycaprolactone polyol and mixtures thereof, and from from about 0.1 to about 0.7 equivalents of at least one aliphatic diol to form a polyurethane.

In some non-limiting embodiments, the present invention provides methods for producing Group H polyurethanes, which comprise the steps of: reacting components comprising: at least one polyisocyanate; at least one polycaprolactone polyol and at least one polyol selected from the group consisting of polyalkylene polyol, polyether polyol and mixtures thereof, with the formation of a polyurethane prepolymer and the interaction of the prepolymer with at least one diol containing from 2 to 18 atoms carbon, with the formation of polyurethane.

Poly (urethaneurea)

Poly (urethane ureas) can be obtained from any of the above polyurethanes of Groups AH by incorporating one or more amine curing agents into the reaction components. The amine functionality of the amine curing agent can react with isocyanate groups to form urea bridges or units within the polyurethane matrix. Appropriate amounts of amine curing agents and reaction conditions are discussed in detail below.

Synthesis of A poly (urethane urea)

Alternatively or additionally, urea bridges or links can be formed within the polymer matrix to the desired degree due to the interaction of the isocyanate functional groups of the polyisocyanate with water. As shown in step 1 of the reaction scheme for the synthesis of A poly (urethane urea) below, isocyanate functional groups are converted to carbamate functional groups by reaction with water. In some non-limiting embodiments, the equivalent NCO: water ratio is in the range of from about 10: 1 to about 2: 1, or from about 5: 1 to about 2: 1, or from about 3: 1 to about 2: 1.

The isocyanate shown in step 1 is a diisocyanate in which R represents any bridging group, for example, aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., which are described in detail above. However, one skilled in the art will understand that an isocyanate may have one or more, two or more, three or more or more isocyanate functional groups, if desired. Examples of suitable isocyanates may be any of the isocyanates discussed above. In some non-limiting embodiments, the polyisocyanate is one or more aliphatic polyisocyanates. In some non-limiting embodiments of the invention, the polyisocyanate is 4,4'-methylene bis (cyclohexyl isocyanate) (such as DESMODUR W).

Removal of carbon dioxide facilitates the conversion of carbamate groups to amine groups. An excess of isocyanate is desirable to provide substantially complete water intake. In addition, it is desirable to remove substantially all of the formed carbon dioxide in order to facilitate the conversion of amine groups. Water can react with a polyisocyanate or polyurethane polyisocyanate prepolymer at temperatures up to about 60 ° C in vacuo. The reduced pressure should be sufficiently low so as not to remove water from the system, and it may be in the range of, for example, from about 10 to about 20 mmHg (from about 1333 to about 2666 Pa) for from about 10 to about 30 minutes. After the reaction is substantially complete, that is, when no additional carbon dioxide is formed, the temperature can be raised to at least about 100 ° C or to about 110 ° C and heated for about 2 to about 24 hours or about 2 hours using 10 ppm or more of a catalyst such as dibutyltin diacetate. After substantially all of the water has reacted with an excess of isocyanate, the resulting amine reacts with the isocyanate substantially instantly.

Synthesis A: Poly (urethane urea)

Stage 1

Stage 2

Stage 3

One skilled in the art is well aware that certain amine curing agents (such as aliphatic amine curing agents containing from 2 to 18 carbon atoms, for example ethylenediamine, diethylenediamine, diaminobutane, PACM, diaminohexane, 1,10-decanediamine) are very reactive capable and unsuitable for use in normal industrial conditions, since the amine functionality very quickly begins to react with the oxygen present in the surrounding air, changing the color of the polymerizate. Aliphatic amine curing agents are generally very hygroscopic and difficult to keep dry. As a rule, aliphatic amines are so reactive that they cannot be used for the manufacture of 100% solids, transparent, slightly colored and having a slight turbidity of plastics.

By forming the amine in situ , as discussed above and as shown in step 2, amines can be generated in situ , which is usually not practiced when used under normal production conditions, without the formation of undesirable by-products, color or turbidity. In addition, the reaction rate can be more easily controlled. Such a reaction can be used for any type of polyisocyanate described above, but is particularly useful for converting aliphatic polyisocyanates to amines, as described above.

As shown in Step 2 above, the amine formed in situ reacts with another isocyanate to form a urea group. Using an excess of polyisocyanate allows the formation of a urea prepolymer with isocyanate functionality. In some non-limiting embodiments, the implementation of the equivalent ratio of the functional groups of NCO: amine is in the range from about 1: 0.05 to about 1: 0.7, or from about 1: 0.05 to about 1: 0.5, or from about 1 : 0.05 to about 1: 0.3. A suitable reaction temperature may be in the range of from about 25 to about 60 ° C. in the presence of a catalyst, such as a tin catalyst. After the water has reacted and after the removal of carbon dioxide, the reaction temperature can be raised to about 90 ° C. over a period of about 2 to about 4 hours. Alternatively, the reaction can be carried out at about 25 ° C for up to about 8 hours until complete. Optionally, one or more of the polyols or diols described above can be introduced into the reaction of interest to form urethane prepolymers with isocyanate functionality, as shown for the synthesis of B poly (urethane urea), described in more detail below.

As shown in step 3 of the poly (urethane urea) synthesis synthesis reaction scheme A, the polyol and / or diol can be reacted with the urea (s) prepolymer (s) with isocyanate functionality to form the poly (urethane ureas) of the present invention. The polyol shown in step 3 may be a diol (m = 2), triol (m = 3) or higher hydroxyl functional material (m = 4 or more), as described above, in which R represents any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc., which are described in more detail above when considering polyols. Examples of suitable polyols can be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and / or pentanediol. Suitable amounts of polyols for reacting with an isocyanate functional urea prepolymer as a polyisocyanate are discussed in detail above. In the above poly (urethane urea), x may range from 1 to about 100, or from about 1 to about 20.

In some non-limiting embodiments, for the formation of poly (urethane urea), the isocyanate functional prepolymer is heated to a temperature of about 90 ° C., the polyol (s) is added and heated to about 90 ° C. The temperature can be raised to about 100 ° C or to about 110 ° C to facilitate alignment, then a vacuum of about 2 to about 4 mm Hg can be applied. for about 3 to about 5 minutes.

To obtain an article, for example, the mixture can be poured or injection molded into glass-coated adhesive molds to form the article of the desired thickness and size. In some embodiments, the molds are preheated to a temperature of about 200 ° F. (93.3 ° C.). The filled mold or cell may be placed in an oven at a temperature of from about 250 ° F (121 ° C) to about 320 ° F (160 ° C) and cured, for example, from about 24 to about 48 hours. The cell can be removed from the furnace and cooled to a temperature of approximately 25 ° C, and the cured polymer can be removed from the mold.

Group I

In some non-limiting embodiments, the present invention provides Group I poly (urethane ureas) comprising a reaction product of components comprising: (a) at least one isocyanate functional urea prepolymer containing the reaction product: (1) at least one polyisocyanate and (2) water; and (b) at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, where these components essentially do not contain or do not contain amine curing agents. Suitable polyisocyanates and branched (e) polyol (s) containing (e) 4 to 18 carbon atoms are described in detail above. If the amine (s) curing agent (s) is present (s) t, then it (they) can (g) t be present in an amount which is defined above as “substantially free”. Any other optional polyols, catalysts, or other additives described above may be included as reaction components in the amounts described above when considering Groups A-H.

In some non-limiting embodiments, the present invention provides methods for producing Group I poly (urethane ureas) which comprise the steps of: (a) reacting at least one polyisocyanate and water to form a urea prepolymer with isocyanate functionality and (b) reacting the reaction product of the components, containing a urea prepolymer with isocyanate functionality, with at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups ppy, wherein said components are substantially free of amine curing agent. The synthesis reaction can be represented as described above for the synthesis of A poly (urethane urea). Optionally, a portion of one or more of the polyols or diols described above can be reacted to form an isocyanate functional urethane prepolymer, which is then reacted with another part of the polyol and / or diol, as shown for synthesis of B poly (urethane urea), which described in more detail below.

Group J

In some non-limiting embodiments, the present invention provides poly (urethane ureas) of Group J containing a reaction product of components comprising: (a) at least one urea prepolymer with isocyanate functionality, containing a reaction product: (1) at least one polyisocyanate, selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and (2) water; and (b) at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups.

Examples of suitable trimers of polyisocyanate and branched polyisocyanates and polyol (s) are discussed above. Any other optional polyols, amine curing agent, catalyst, and other additives described above may be included in the reaction components in amounts described above when considering the above Groups AH. In some non-limiting embodiments, the reaction components essentially do not contain or do not contain amine curing agents described above.

In other non-limiting embodiments, the present invention provides methods for producing poly (urethane ureas) which comprise the steps of: (a) reacting at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates and water to form a urea prepolymer with an isocyanate functionality and (b) the interaction of the reaction product of components containing a urea prepolymer with isocyanate functionality with at least one aliphatic floor ol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups wherein said components are substantially free of amine curing agent.

The synthesis reaction can be represented as described above for the synthesis of A poly (urethane urea). Optionally, a portion of one or more of the polyols or diols described above can be reacted to form an isocyanate functional urethane prepolymer, which is then reacted with another part of the polyol and / or diol, as shown for synthesis of B poly (urethane urea), which described in more detail below.

Synthesis Of Poly (Urethane Urea)

As shown generally below for the synthesis of B poly (urethane ureas), in other non-limiting embodiments of the invention, urea bridges or links can be formed within the polyurethane matrix to the desired degree due to the interaction of the polyisocyanate (s) and part of the polyol (s) to form at least at least one urethane prepolymer with isocyanate functionality and then the interaction of the urethane (s) prepolymer (s) with isocyanate functionality with water. As shown in step 1 of the reaction scheme for the synthesis of poly (urethane urea) below, part of the polyol (s) and / or diol (s) can be reacted with polyisocyanate (s) to form at least one urethane prepolymer with isocyanate functionality . In some non-limiting embodiments, the equivalent functional group ratio of NCO: OH is in the range of from about 1: 0.05 to about 1: 0.7, or from about 1: 0.05 to about 1: 0.5, or from about 1: 0.05 to about 1: 0.3. It is desirable to use an excess of isocyanate to ensure substantially complete conversion of the hydroxyl groups to urethane groups.

The isocyanate shown in step 1 is a diisocyanate in which R is any bridging group such as aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., which are described in more detail below. However, one of skill in the art will understand that an isocyanate may have one or more, two or more, three or more or more isocyanate functional groups, if desired. Examples of suitable isocyanates can be any of the polyisocyanates described above. In some non-limiting embodiments, the polyisocyanate is one or more aliphatic polyisocyanates. In some non-limiting embodiments of the invention, the polyisocyanate is 4,4'-methylene bis (cyclohexyl isocyanate) (such as DESMODUR W).

The polyol shown in step 1 may be a diol (m = 2), triol (m = 3) or a higher hydroxyl functional material (m = 4 or more), as described above, in which R represents any bridging group, such as aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc., which are described in more detail above when considering polyols. Examples of suitable polyols can be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and / or pentanediol. Optionally, one or more catalysts, such as those described above, may be used to facilitate the reaction. The polyisocyanate can be reacted with the polyol to form an isocyanate-functional urethane prepolymer by loading the reactants into the reactor and adding about 10 ppm or more of a catalyst, such as a tin, bismuth or zirconium catalyst. The mixture can be heated at a temperature of about 100 ° C or about 110 ° C for from about 2 to about 4 hours, until all hydroxyl functionalities have reacted. FTIR spectroscopy data can be used to determine the extent of the reaction.

Urea bridges or links can be formed within the polyurethane matrix to the desired degree due to the interaction of isocyanate functional groups of the urethane prepolymer with isocyanate functionality with water. As shown in step 2 of the reaction scheme for the synthesis of B poly (urethane urea) below, isocyanate functional groups are converted to carbamate functional groups by reaction with water. In some non-limiting embodiments, the equivalent NCO: water ratio is in the range of from about 1: 0.05 to about 1: 0.7, or from about 1: 0.05 to about 1: 0.5, or from about 1: 0, 05 to about 1: 0.3.

Removal of carbon dioxide facilitates the conversion of carbamate groups to amine groups. An excess of isocyanate is desirable to provide substantially complete water intake. In addition, it is desirable to remove substantially all of the formed carbon dioxide in order to facilitate conversion to amine groups. To prevent the removal of water in a vacuum, the reaction can be started at a temperature of approximately 25 ° C, then the temperature is raised to approximately 60 ° C when a vacuum is connected to remove carbon dioxide. After the cessation of carbon dioxide formation, the temperature can be raised to at least about 100 ° C. or about 110 ° C. for about 2 to about 4 hours.

As discussed above, some amine curing agents (such as aliphatic amine curing agents) are highly reactive and not suitable for use under normal manufacturing conditions. By forming the amine in situ , as discussed above and as shown in step 2, amines can be generated in situ , which is usually not practiced for use under normal production conditions, without generating undesired reaction by-products. In addition, the reaction rate can be more easily controlled. Such a reaction can be used for any type of polyisocyanate described above, but is particularly useful for converting aliphatic polyisocyanates to amines, as described above.

As shown in step 3 below, the amine formed in situ reacts with another isocyanate to form a urea group. The use of excess polyisocyanate provides the formation of a urethane urea prepolymer with isocyanate functionality. An isocyanate-functional urea urea prepolymer can be prepared by reacting a stoichiometric excess of the polyisocyanate with an amine under substantially anhydrous conditions at a temperature in the range of from about 25 to about 150 ° C. or at about 110 ° C. until the reaction between the isocyanate groups and the amine groups is substantially will end. The polyisocyanate and amine components can be reacted in such proportions that the ratio of the number of isocyanate groups to the number of amine groups is in the range of from about 1: 0.05 to about 1: 0.7, or within the range of from about 1: 0.05 to approximately 1: 0.3.

As shown in step 4 of the reaction scheme for the synthesis of poly (urethane urea) below, an isocyanate functional urea urea prepolymer can be reacted with another part of the polyol and / or diol to form the poly (urethane urea) of the present invention. The polyol shown in step 4 may be a diol, triol or higher hydroxyl functional material, as described above, in which R represents any bridging group, such as an aliphatic, cycloaliphatic, aromatic, heterocyclic group, etc., which in more detail described above when considering polyols. Examples of suitable polyols can be any of the above polyols. In some non-limiting embodiments of the invention, the polyol may be trimethylolpropane and butanediol and / or pentanediol. Appropriate amounts of polyols to react with a urethane urea prepolymer with isocyanate functionality as a polyisocyanate are discussed in detail above.

An isocyanate functional urea urea prepolymer can be reacted with another part of the polyol and / or diol (n = 2 or more) under substantially anhydrous conditions at a temperature in the range of from about 120 to about 160 ° C, while the reaction between the isocyanate groups and hydroxyl groups essentially will not end. The components of the urethane urea prepolymer with isocyanate functionality and the polyol (s) and / or diol (s) can be reacted in such proportions that the ratio of the number of isocyanate groups to the number of hydroxyl groups is in the range from about 1.05: 1 to about 1: 1 . In the poly (urethane urea), the K y groups may range from 1 to about 500 and higher, or from about 1 to about 200.

The curing temperature depends on the glass transition temperature of the final polymer. In some embodiments, for full cure, the cure temperature must be greater than the glass transition temperature. For example, the curing temperature may range from about 140 ° C to about 180 ° C or from about 143 ° C to about 180 ° C.

Synthesis B: Poly (urethane urea)

Stage 1

Stage 2

Stage 3

Stage 4

Group K

In some non-limiting embodiments, the present invention provides Group K poly (urethane ureas) containing a reaction product of components comprising: (a) at least one isocyanate functional urea urea prepolymer containing the reaction product: (1) at least one urethane prepolymer with isocyanate functionality containing the reaction product: (i) a first amount of at least one polyisocyanate and (ii) a first amount of at least one branched polyol; and (2) water, with the formation of a urethane-urea prepolymer with isocyanate functionality and (b) a second amount of at least one polyisocyanate and a second amount of at least one branched polyol.

Examples of suitable polyisocyanates and polyol (s) are discussed above. Any other optional polyols, amine curing agents, catalysts, and other additives described above may be included in the reaction components in amounts described above when considering the above Groups A-G. In some non-limiting embodiments, the reaction components are substantially free or free of the amine curing agent described above, or free of the amine curing agent.

In other non-limiting embodiments, the present invention provides methods for producing Group K poly (urethane ureas), which comprise the steps of: (a) reacting at least one polyisocyanate and at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, with the formation of an urethane prepolymer with isocyanate functionality; (b) reacting an urethane prepolymer with isocyanate functionality with water and a polyisocyanate to form a urethane urea prepolymer with isocyanate functionality; and (c) reacting a reaction product of components containing a urethane urea prepolymer with isocyanate functionality with at least one aliphatic polyol containing from 4 18 carbon atoms and at least 2 hydroxyl groups, where these components essentially do not contain an amine curing agent. The synthesis reaction can be represented as described above for the synthesis of poly (urethane urea).

Group L

In other non-limiting embodiments, the present invention provides poly (urethane ureas) of Group L containing a reaction product of components comprising: (a) at least one urethane urea prepolymer with isocyanate functionality containing the reaction product: (1) at least one urethane prepolymer with isocyanate functionality containing the reaction product: (i) a first amount of at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched fields zocyanates, wherein the polyisocyanate contains at least three isocyanate functional groups; and (ii) a first amount of at least one aliphatic polyol; and (2) water, with the formation of a urethane-urea prepolymer with isocyanate functionality and (b) a second amount of at least one polyisocyanate and a second amount of at least one aliphatic polyol.

Examples of suitable trimers of polyisocyanates and branched polyisocyanates containing at least three isocyanate functional groups and polyol (s) are discussed above. Any other optional polyols, amine curing agent, catalysts, or other additives described above may be included as reaction components in the amounts described above when considering the above Groups A-G. In some non-limiting embodiments, the reaction components are substantially free or free of the amine curing agent described above.

In some non-limiting embodiments, the present invention provides methods for producing a poly (urethane urea) of group L, which comprise the steps of: (a) reacting at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, and at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups, with the formation of an urethane prepolymer with isocyanate functionality; (b) reacting an urethane prepolymer with isocyanate functionality with water and a polyisocyanate to form a urethane urea prepolymer with isocyanate functionality; and (c) reacting a reaction product of components containing a urethane urea prepolymer with isocyanate functionality with at least one aliphatic polyol containing from 4 18 carbon atoms and at least 2 hydroxyl groups; where these components essentially do not contain or do not contain amine curing agent. The synthesis reaction can be represented as described above for the synthesis of poly (urethane urea).

As discussed above, poly (urethane ureas) can be prepared by incorporating one or more amine curing agents into the reaction components. The amine functionality of the amine curing agent can be reacted with isocyanate groups to form urea bridges or units within the polyurethane matrix.

Group M

In other non-limiting embodiments, the present invention provides poly (urethane ureas) of Group M comprising a reaction product of components comprising: about 1 equivalent of at least one polyisocyanate; from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; from about 0.1 to about 0.9 equivalents of at least one aliphatic diol containing from 2 to 18 carbon atoms; and at least one amine curing agent, wherein said components are substantially free or free of polyester polyol and polyether polyol.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols and amine curing agents for use as reaction components for the preparation of Group M polyurethanes are discussed in detail above when considering Group A.

In some non-limiting embodiments, the amount of branched polyol used to produce Group M polyurethane may be from about 0.3 to about 0.98 equivalents, in other non-limiting embodiments from about 0.5 to about 0.98 equivalents, and in other non-limiting embodiments about 0.3, or about 0.9, or about 0.98 equivalents.

In some non-limiting embodiments, the amount of aliphatic diols used to prepare Group M polyurethane may be from about 0.1 to about 0.7 equivalents, in other non-limiting embodiments from about 0.1 to about 0.5 equivalent, and in other non-limiting embodiments is approximately 0.3 equivalent.

In some non-limiting embodiments, the amount of amine curing agent used to produce Group M polyurethane may be from about 0.1 to about 0.9 equivalents, in other non-limiting embodiments from about 0.1 to about 0.7 equivalents, and in other non-limiting options is approximately 0.3 equivalent.

As for the poly (urethane ureas) of Group M, the expression "essentially does not contain polyester polyol and polyether polyol" means that the polyester polyol and polyether polyol can be present as reaction components in appropriate amounts, as described above for Group A polyurethane, or reaction the components may not contain one or both of polyester polyol and polyether polyol.

Any other optional polyols, catalysts, or other additives described above may be included as reaction components in the amounts described above when considering the above Groups A — H.

In other non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which include the step of simultaneously reacting components comprising: at least one polyisocyanate; at least one branched polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; at least one aliphatic diol containing from 2 to 18 carbon atoms; and an amine curing agent, wherein said components are substantially free or free of polyester polyol and polyether polyol.

Group N

In other non-limiting embodiments, the present invention provides poly (urethane ureas) of Group N containing a reaction product of components comprising: (a) at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates, wherein the polyisocyanate contains at least , three isocyanate functional groups; (b) from about 0.1 to about 0.9 equivalents of at least one polyol containing from 4 to 18 carbon atoms and at least 2 hydroxyl groups; and (c) at least one amine curing agent, wherein said components are substantially free or free of polyester polyol and polyether polyol.

Non-limiting examples of suitable polyisocyanates, branched polyols containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols and amine curing agents for use as reaction components for the preparation of Group N polyurethanes are discussed in detail above when considering Groups A- FROM.

In some non-limiting embodiments, the amount of branched polyol used to prepare the Group N polyurethane may be from about 0.3 to about 0.98 equivalent, in other non-limiting embodiments from about 0.5 to about 0.98 equivalent, and in other non-limiting embodiments is about 0.3, or about 0.9, or about 0.98 equivalents.

In some non-limiting embodiments, the amount of aliphatic diols used to prepare Group N polyurethane may be from about 0.1 to about 0.7 equivalent, in other non-limiting embodiments from about 0.1 to about 0.5 equivalent, and in other non-limiting embodiments is approximately 0.3 equivalent.

In some non-limiting embodiments, the amount of amine curing agent used to prepare Group N polyurethane may be from about 0.1 to about 0.7 equivalent, in other non-limiting embodiments from about 0.1 to about 0.5 equivalent, and in other non-limiting options is approximately 0.3 equivalent.

As for the poly (urethane ureas) of Group N, the expression “substantially free of polyester polyol and polyether polyol” means that the polyester polyol and polyether polyol can be present as reaction components in appropriate amounts, as described above for Group A polyurethane, or reaction the components may not contain one or both of polyester polyol and polyether polyol.

Any other optional polyols, catalysts, or other additives described above may be included as reaction components in the amounts described above when considering the above Groups A — H.

In other non-limiting embodiments, the present invention provides methods for producing poly (urethane urea), which comprise the step of simultaneously reacting components comprising: at least one polyisocyanate selected from the group consisting of trimers of polyisocyanate and branched polyisocyanates; at least one aliphatic polyol containing from 4 to 18 carbon atoms and at least 3 hydroxyl groups; at least one aliphatic diol containing from 2 to 18 carbon atoms; and an amine curing agent, wherein said components are substantially free or free of polyester polyol and polyether polyol.

In some embodiments, poly (urethaneurea) Groups I-N of the present invention may be thermoset.

Group O

In some non-limiting embodiments, the present invention provides polyurethane materials comprising a first part of crystalline particles that are self-oriented and bonded together to fix their orientation along the first crystallographic direction, and a second part of crystalline particles that are self-oriented and bonded together to fix their orientation along the second crystallographic direction moreover, the first crystallographic direction differs from the second crystallographic direction, where these crystalline particles comprise at least about 30% of the total volume of the polyurethane material.

Particles interact with each other or with the surface of the base, aligning their crystallographic axis in one, two or three directions. Used in this case, the definition of "aligning" or "aligned" with respect to crystalline particles means that the particles of the specified crystalline part are arranged in a row, usually of a fixed position and orientation. The preferred degree of alignment will depend on the intended use of the material. For alignment, it is desirable that the particles have the same shape with dominant flat surfaces in a suitable orientation, for example, perpendicular or parallel to the desired alignment direction.

In some non-limiting embodiments of the invention, the first part of the crystalline particles is aligned in two directions. In some non-limiting embodiments of the invention, the first part of the crystalline particles is aligned in three directions. In some embodiments, crystalline particles are aligned along a segment in the range of from about 1 to about 50 nm along any direction.

In some non-limiting embodiments of the invention, the second part of the crystalline particles is aligned in two directions. In some non-limiting embodiments of the invention, the second part of the crystalline particles is aligned in three directions.

The crystalline particles of the present invention have at least “self-leveling” morphology. Used in this case, the definition of "self-leveling" morphology includes any particles that are capable of self-organization with the formation of a polycrystalline structure, where single particles are located along at least one crystallographic direction in areas of higher density and order, for example, the type of lamellas. Examples of crystalline morphologies of crystalline particles with self-leveling morphology are cubic particles, hexagonal plates, hexagonal fibers, rectangular plates, rectangular particles, triangular plates, square plates, tetraerds, cubes, octagons, and mixtures thereof.

A self-leveling morphology can exhibit an orientation that can be up to about 10 degrees from the desired direction of alignment, while still fixing the desired properties sufficiently. Therefore, particles possessing such morphologies are particles that essentially have the necessary morphology. For example, for particles that are cubic, the particles should not be flawless cubes. The axes should neither be perfectly at an angle of 90 ° C nor be exactly the same in length. Corners can also be cut from particles. Moreover, the definitions of “cube” or “cubic” are intended to make reference to morphology, and are not intended to limit particles to systems of cubic crystals. Indeed, single crystalline particles that have a rhombic, tetragonal or rhombohedral crystalline structure can also be used as cubes if they possess a certain cubic morphology. In other words, any substantially orthogonal single crystalline particles in which the surfaces are substantially square, substantially triangular, or both that have a substantially cubic morphology are considered to be cubic from the perspective of the present invention.

Crystalline particles can be aligned into monolithic structures containing one layer of crystals or multiple layers of crystals. The layer or layers are generally flat, although the layers may correspond to curved surfaces or complex geometries depending on the shape of the support base material during formation and during curing of the polyurethane.

The polycrystalline materials of the present invention are obtained by densifying and aligning a plurality of single crystalline particles in a line to achieve one-, two- or three-dimensional alignment. In some non-limiting embodiments, the particles may have the ability to self-group in a line during aging (aging) or during heat treatment. In some non-limiting embodiments, in order to obtain a solid diffusion level sufficient to bond adjacent particles together, temperatures above about half the melting point, which in most cases are usually in the range of from about 35 ° C to about 100 ° C, are required. The selected temperature range will depend on the material that needs to be joined, but can be easily determined by a person skilled in the art without undue experimentation within a given range. The production steps can be repeated to form a polycrystalline material having multiple layers of aligned particles. The resulting material is essentially a three-dimensional object with one, two or three spatial alignments of single crystalline particles within the object.

FIG. 4 is a TEM photomicrograph showing a polyurethane casting obtained in accordance with Example A Formulation 2. Said casting was analyzed using TEM two weeks after polymerization of the polyurethane. The casting was stored at room temperature (approximately 25 ° C) for two weeks. As shown in FIG. 4, no distinguishable regions located in a row of crystals are observed.

FIG. 5 is a TEM photomicrograph showing a polyurethane casting in accordance with Example A Formulation 2. Said casting was analyzed using TEM three weeks after polymerization of the polyurethane. The casting was stored at room temperature (approximately 25 ° C.) for three weeks. As shown in FIG.5, there is an initial formation of crystalline domains.

FIG. 6 is a TEM photomicrograph showing a polyurethane casting according to Example A Formulation 2. Said casting was analyzed using TEM seven months after polymerization of the polyurethane. The casting was stored at room temperature (approximately 25 ° C) for seven months. In the micrograph of FIG. 6, a region of crystals arranged in a row is visible, usually parallel to the arrows.

FIG.7 is an electronic diffraction pattern of the polyurethane of Example A, Formulation 2, stored at room temperature (approximately 25 ° C.) for seven months. Bright spots in the figure represent reflections from the planes of the crystal lattice, which are approximately 8 nm × approximately 4 nm in size.

FIG. 8 is a TEM photomicrograph showing a polyurethane casting according to Example A, Formulation 2, obtained after incubation at room temperature for approximately 7 months. The micrograph of FIG. 8 shows many regions or domains arranged in a row of crystals, usually parallel to the arrows, and the domains are oriented in different directions and exhibit a higher domain density than samples held for three weeks.

FIGURE 9 is a TEM photomicrograph showing the first part of a polyurethane casting according to Example A, Formulation 2, obtained after incubation at room temperature for about two to four weeks. The casting was stored at room temperature for two to four weeks. As shown in FIG.9, distinguishable areas located in a row of crystals is not observed.

FIGURE 10 is a TEM photomicrograph showing the second part of a polyurethane casting according to Example A, formulation 2 shown in FIG. 9. As can be seen in the limited area of FIG. 10, the initial formation of crystalline domains is observed.

The samples shown in FIGS. 9 and 10 have a Gardner impact resistance of 180 inch · lb.

FIGURE 11 is a TEM photomicrograph showing a polyurethane casting according to Example A Formulation 2. Said casting is analyzed using TEM about two to about four weeks after polymerization of the polyurethane. The casting was stored at room temperature for two to four weeks. On microphotographs FIGURE 11 in limited areas visible areas located in a row of crystals.

12 is a TEM photomicrograph showing the first part of a polyurethane casting in accordance with Example A, Formulation 2, obtained after incubation at room temperature for approximately 7 months. On microphotographs FIG.12 shows a large region or domain located in a row of crystals.

FIGURE 13 is a TEM photomicrograph showing the second part of a polyurethane casting according to Example A, Formulation 2, shown in FIGURE 12. The micrograph of FIG.13 shows many regions and domains arranged in a row of crystals, and the domains are oriented in different directions and exhibit a higher density than samples aged for a shorter period of time.

The samples shown in FIGS. 12 and 13 have a Gardner impact resistance of 640 inch · lb.

FIG. 14 is a graph of heat flux as a function of temperature when measured using differential scanning calorimetry (DSC) for castings of polyurethane in accordance with Example A, Formulation 2, measured after aging under normal conditions for two weeks, three months, and seven months respectively. The enthalpy of the melting endotherm of the crystalline domains grows in time, showing a change in the morphology of the polymer and microstructure in time, even if the polymer is glassy and highly crosslinked with a glass transition temperature of 235 ° F (113 ° C). As the number and size of crystalline domains increases, the enthalpy of melting increases. Gardner impact resistance increases with time. After two weeks, Gardner impact resistance is 180 inches · lb. After three months, Gardner impact resistance is 380 in · lb. After seven months, Gardner impact resistance is 640 inches · lb.

15 is a graph of Gardner impact resistance as a function of Young's modulus for polyurethane castings in accordance with Example A, Formulations 2 and 1, measured after incubation under normal conditions for seven months and one year, respectively. After seven months, in the case of formulation 2, the impact resistance according to Gardner is 640 inch · lb. After one year, in the case of formulation 1, the Gardner impact resistance is 400 inch · lb.

In some non-limiting embodiments, the implementation of the polyurethane material includes a monolithic agglomerate of the first part of the crystalline particles with small-angle grain boundaries between them, bonded together by the polymer phase.

In some non-limiting embodiments, the implementation of the polyurethane material includes a monolithic agglomerate of the second part of crystalline particles with small-angle grain boundaries between them, bonded together by the polymer phase.

In some non-limiting embodiments, the polyurethane material includes a monolithic agglomerate of the first part of crystalline particles with small-angle grain boundaries and, as a rule, with an amorphous phase between them.

In some non-limiting embodiments, the polyurethane material comprises a monolithic agglomerate of the second part of crystalline particles with small-angle grain boundaries and, as a rule, with an amorphous phase between them.

In some non-limiting embodiments, the thickness of the first portion of the crystalline particles is less than about 50 nm. In some non-limiting embodiments, the thickness of the second part of the crystalline particles is less than about 50 nm. The length and width, respectively, of the first part can vary, for example about 4 nm at about 8 nm.

In some non-limiting embodiments, the thickness of the first portion of the crystalline particles can range from about 10 nm to about 100 nm. In some non-limiting embodiments, the thickness of the second portion of the crystalline particles can range from about 4 to about 50 nm. The length and width, respectively, of the second part can vary, for example about 4 nm at about 8 nm.

In some non-limiting embodiments, crystalline particles comprise at least about 30% of the total material. In other non-limiting embodiments, the implementation of the crystalline particles comprise at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% of the total material. The percentage of crystalline particles can be determined using DSC. For example, a product obtained from formulation 2 described below, aged under normal conditions (approximately 25 ° C.) for 7 months, has a crystallinity of approximately 43% vol.

In some non-limiting embodiments, the polyurethane comprises a reaction product of components comprising: (a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate); (b) about 0.3 equivalent of trimethylolpropane; and (c) about 0.7 equivalent of butanediol or pentanediol. In some non-limiting embodiments, butanediol is 1,4-butanediol. In some non-limiting embodiments, pentanediol is 1,5-pentanediol.

In some non-limiting embodiments, the impact resistance of the above-described polyurethanes and poly (urethane ureas) of Groups AM in accordance with the present invention can be improved by aging or heat treatment.

In some non-limiting embodiments, the implementation of the polyurethane material after education can be aged for at least about 2 weeks. In some non-limiting embodiments, the implementation of the polyurethane material after formation can be aged for at least about 2 months. In some non-limiting embodiments, the polyurethane material after formation can be aged for at least about 7 months.

In some non-limiting embodiments, the polyurethane material after formation is heated at a temperature of from about 90 ° C to about 150 ° C or from about 200 ° F (93 ° C) to about 290 ° F (143 ° C) for about 1 to about 24 hours. In some non-limiting embodiments, the polyurethane material is heated at a temperature sufficient to induce mobility of the grain boundary so that the particles grow until a collision with the grain boundaries of adjacent crystals prevents additional growth. The end result is a polycrystalline microstructure, the grains of which for all practical purposes are arranged in a row in two or three directions so that they behave like one crystal relative to some desired property.

Impact resistance or flexibility can be measured using a number of conventional techniques known to those skilled in the art. The flexibility of the materials can be measured using a Gardner impact test using a Gardner impact test instrument in accordance with ASTM-D 5420-04, which consists of a 40-inch (101.6 cm) aluminum tube in which An 8- or 16-pound (17.6 or 35.2 kg) mass falls from various heights onto a metal dart located on the base under test with a sample size of 2 × 2 × 1/8 inch (5.1 × 5, 1 × 0.3 cm). In a non-limiting embodiment, the impact resistance data for a Gardner impact test is at least about 65 inch · lb (7.3 J) or from about 65 inch · lb (7.3 J) to about 640 inch · lb ( 72 J).

Alternatively, impact resistance can be measured using the Dynatup Test in accordance with ASTM-D 3763-02, which consists of a high-speed test using a load cell that measures the total energy absorption in the first microseconds of shock. Impact strength can be measured in joules. In a non-limiting embodiment, the base may have an impact strength of at least about 35 J or from about 35 J to about 105 J.

Group P

In some non-limiting embodiments, the present invention provides a polyurethane powder coating composition. Powder coating compositions can be prepared from any polyurethanes or poly (urethane ureas) Groups A-N described in detail above.

In non-limiting embodiments, the present invention provides methods for preparing a polyurethane powder coating composition, which comprise the steps of: reacting at least one polyisocyanate with at least one aliphatic polyol to form, as a rule, a solid prepolymer with hydroxyl functionality; melting a prepolymer with hydroxyl functionality; melting at least one, typically solid polyisocyanate to form a molten polyisocyanate; mixing the molten prepolymer with hydroxyl functionality and the molten polyisocyanate to form a mixture and curing the mixture to form, as a rule, a solid powder coating composition.

Typically, a solid prepolymer with hydroxyl functionality can be obtained by reacting the polyisocyanate (s) with an excess of the aliphatic polyol (s) and catalyst in the amounts described above, and by heating the prepolymer at a temperature of about 140 ° C or at a temperature of about 150 ° From about 180 ° C. for from about 1 to about 24 hours, to facilitate the substantially complete completion of the reaction of the components and the formation of a typically solid prepolymer.

In some non-limiting embodiments, the polyisocyanate is branched or trimer, as discussed above, and the aliphatic polyol is an aliphatic diol containing from 4 to 18 carbon atoms or 4 or 5 carbon atoms, such as propanediol, butanediol, cyclohexane dimethanol, 1, 10-decanediol and / or 1.12-dodecanediol. In other non-limiting embodiments of the invention, the polyisocyanate may be any of the polyisocyanates discussed above, and the aliphatic polyol may be a branched diol containing from 4 to 18 carbon atoms, such as trimethylolpropane.

The equivalent ratio of isocyanate functional groups to hydroxyl functional groups is in the range of from about 1: 0.9 to about 1: 1.1, or about 1: 1.

Typically, the solid polyisocyanate can be melted, for example, by heating at a temperature of from about 35 ° C to about 150 ° C for from about 2 to about 24 hours to form a molten polyisocyanate. The molten hydroxyl functional prepolymer and the molten polyisocyanate are mixed and cured to form a generally homogeneous mixture suitable for forming a powder coating, which is discussed below. The equivalent ratio of the isocyanate functional groups of the polyisocyanate to the hydroxyl functional groups of the prepolymer may be in the range of from about 1.05: 1 to about 0.95: 1, or about 1: 1.

In other non-limiting embodiments, the present invention provides methods for producing a polyurethane powder coating composition, comprising the steps of: reacting at least one polyisocyanate with at least one aliphatic polyol to form, as a rule, a solid prepolymer with hydroxyl functionality; dissolving the prepolymer with hydroxyl functionality in a first solvent to form a first solution; dissolving at least one, typically solid polyisocyanate in a second solvent, which is the same solvent or compatible with the first solvent, to form a second solution; mixing the first and second solutions and removing substantially all of the solvent to form, as a rule, a solid powder coating composition.

In some non-limiting embodiments, the implementation of the polyisocyanate (s) is (are) branched (s) or is (s) a trimer, as discussed above, and the aliphatic polyol is an aliphatic diol containing from 4 to 18 carbon atoms or 4 or 5 carbon atoms, such as propanediol and / or butanediol. In other non-limiting embodiments of the invention, the polyisocyanate may be any of the polyisocyanates discussed above, and the aliphatic polyol may be a branched diol containing from 4 to 18 carbon atoms, such as trimethylolpropane.

Typically, a solid prepolymer with hydroxyl functionality can be prepared by reacting the polyisocyanate (s) with an excess of aliphatic (s) polyol (s) and catalyst, the types and quantities of which are described above. The hydroxyl functional prepolymer is dissolved in the first solvent to form the first solution. The solvent may be any solvent capable of dissolving a prepolymer with hydroxyl functionality, such as a dipolar aprotic solvent, for example m-pyrol (N-methyl-2-pyrrolidone), N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide (DMSO) , methylene chloride, dichlorobutane, cyclohexanone, dimethylformamide and / or acetonitrile. The amount of solvent may range from about 20 to about 95 wt.% Based on the weight of the solids of the prepolymer with hydroxyl functionality.

Typically, the solid polyisocyanate is dissolved in a second solvent, which is the same solvent or compatible with the first solvent, to obtain a second solution. The solvent may be any solvent capable of dissolving a typically solid polyisocyanate, such as a dipolar apotonic solvent, for example m-pyrrole (N-methyl-2-pyrrolidone), N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide (DMSO), methylene chloride, dimethylformamide and / or acetonitrile. The amount of solvent may range from about 20 to about 95 wt.% Based on the weight of the polyisocyanate solids.

The first and second solutions are mixed and substantially all of the solvent is removed, for example, by vacuum in a furnace to form an essentially solid powder suitable for use as a coating composition. The powder may be crushed or finely ground, if necessary.

A curable powder coating composition that can be used in the present invention is usually prepared by dry mixing the polymer, for example polyurethane or poly (urethane urea), a crosslinking agent (if present), particles and additives such as degassing agents, agents for yielding agents and catalysts in a mixer, for example a Henshel paddle mixer. The mixer operates for a period of time sufficient to obtain a dry homogeneous mixture of the materials loaded into it. The dry homogeneous mixture is then mixed in the melt in an extruder, for example in a twin-screw extruder with joint rotation of the screws, which operates in a temperature range sufficient to melt the components, but to prevent gel formation.

Optionally, a curable powder coating composition of the present invention can be melt blended in two or more stages. For example, a first melt mixture is prepared in the absence of a curing catalyst. A mixture of the second melt is prepared at a lower temperature from a dry mixture of the first melt and the curing catalyst. The melt-mixed, curable, powder coating composition is typically ground to an average particle size, for example from 15 to 30 microns.

On the other hand, the powder coating compositions of the present invention can be obtained by mixing and extruding the ingredients, as described above, but without particles. Particles can be added to the formulation as a post-additive by simply mixing the particles into a ground powder coating composition, for example by mixing using a Henschel mixer. In some non-limiting embodiments of the invention, the powder coating composition is suspended in a liquid medium, such as water, which can be applied by spraying.

Group Q

In some non-limiting embodiments, the compositions of the present invention may further include one or more types of reinforcing materials. Such reinforcing materials may be present in any desired physical form, for example in the form of particles, including, but not limited to, in the form of nanoparticles, agglomerates, fibers, finely chopped fibers, mats, etc.

Reinforcing materials may be formed from materials selected from the group consisting of polymeric inorganic materials, non-polymeric inorganic materials, polymeric organic materials, non-polymeric organic materials, their composites, and mixtures thereof that are chemically different from polyurethane or poly (urethane urea). Used in this case, the definition of "chemically different" from polyurethane or poly (urethane urea) means that the reinforcing material has at least one other atom or has a different arrangement of atoms compared to polyurethane or poly (urethane urea).

As used herein, the term “polymeric inorganic material” means a polymeric material having a repeat chain backbone based on an element or elements other than carbon (see publication: James Mark et al. Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series (1992 ), p. 5, which is incorporated herein by reference). Moreover, the term “polymeric organic materials” used in this case means synthetic polymeric materials, semi-synthetic polymeric materials and natural polymeric materials, which all have a carbon-based repeating unit.

As used herein, the term “organic material” means carbon-containing compounds, where carbon is generally bound to itself and hydrogen and often to other elements, and also excludes binary compounds such as carbon oxides, carbides, carbon sulfide, etc .; such trinomial compounds as metal cyanides, metal carbonyls, phosgene, carbonyl sulfide and others; and carbon-containing ionic compounds, such as metal carbonates, for example calcium carbonate and sodium carbonate (see R. Lewis, Sr. Hawley's Condensed Chemical Dictionary (12th Ed., 1993), pp. 761-762; and M. Silberberg, Chemistry The Molecular Nature of Matter and Change (1996), p. 586, which are incorporated herein by reference).

Used in this case, the definition of "inorganic material" means any material that is not organic material.

Used in this case, the definition of "composite material" means a combination of two or more different materials. For example, a composite particle may be formed from a primary material that is coated, clad, or encapsulated by one or more secondary materials to form a composite particle that has a softer surface. In some non-limiting embodiments, particles formed from composite materials can be obtained from a primary material that is coated, clad, or encapsulated using various forms of the primary material. For more information on particles that can be used in the present invention, see G. Wypych, Handbook of Fillers, 2-nd Ed., (1999), p. 15-202, which is incorporated herein by reference.

Reinforcing materials suitable for use in the compositions of the present invention may include inorganic elements or compounds known in the art. Suitable non-polymeric, inorganic reinforcing materials may be formed from ceramic materials, metallic materials, and mixtures of any of the listed materials. Non-polymeric, inorganic materials that may be useful in forming the reinforcing materials of the present invention include inorganic materials selected from the group consisting of graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates and hydroxides. Suitable ceramic materials are metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates and mixtures of any of the foregoing. Non-limiting examples of suitable metals are molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys, and mixtures of any of the above metals. A non-limiting example of metal nitrides is, for example, boron nitride; a non-limiting example of metal oxides is, for example, zinc oxide; non-limiting examples of suitable metal sulfides are, for example, molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; non-limiting examples of metal silicates are, for example, aluminum silicates and magnesium silicates, for example vermiculite. In some non-limiting embodiments, the implementation of the reinforcing material essentially does not contain (less than 5 wt.% Or less than 1 wt.%) Or does not contain fillers such as sodium carbonate, calcium carbonate, silicates, alginates, carbon black, and metal oxides, such like titanium oxide, silicon dioxide and zinc oxide.

In some non-limiting embodiments, the reinforcing materials may include a core of essentially one inorganic oxide, such as colloidal, colloidal or amorphous silica, alumina or colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttrium oxide, zirconium, for example colloidal or amorphous zirconium oxide, and mixtures of any of these components; or an inorganic oxide of one type onto which an organic oxide of another type is applied. In some non-limiting embodiments, the reinforcing materials should not greatly affect the optical characteristics of the cured composition. Used in this case, the definition of "transparent" means that the cured coating has a haze index (BYK Haze index) of less than 50 when measured using a BYK / Haze Gloss Instrument.

The composition may include precursors suitable for in situ formation of silica particles by a sol-gel process. The composition in accordance with the present invention may contain alkoxysilanes, which can be hydrolyzed to form particles of silicon dioxide in situ . For example, tetraethylorthosilicate can be hydrolyzed with an acid, such as hydrochloric acid, and condensed to form silica particles. Other useful particles are surface modified silicas, for example, those described in US Pat. No. 5,853,809 (column 6, line 51 to column 8, line 43, incorporated by reference).

In the present invention can be used sols, such as organosols, reinforcing particles. Such sols can be a wide range of colloidal silicon dioxide with small particles having an average particle size in the ranges described below. Colloidal silicas can be surface modified during or immediately after particle formation. Such surface-modified silicas can have chemically bonded carbon-containing residues on their surface, as well as groups such as anhydrous SiO ₂ groups and SiOH groups, various ionic groups physically associated with or chemically bonded to the surface of silicon dioxide, adsorbed organic groups or combinations any of the above components, depending on the desired characteristics of the particles of silicon dioxide. Such surface modified silicas are described in detail in US Pat. No. 4,680,204, which is incorporated herein by reference. Such colloidal silicas with small particles are readily available, essentially colorless and have refractive indices that make it possible to incorporate them into the composition, which without additional pigments or components, which are known in the art, color and / or reduce the transparency of such compositions, results in colorless, transparent compositions or coatings.

Other suitable non-limiting examples of reinforcing materials are colloidal silicas, such as silicas, commercially available from Nissan Chemical Company under the trade name ORGANOSILICASOLS ^TM , such as ORGANOSILICASOLS ^TM MT-ST, and from Clariant Corporation, such as HIGHLINK ^TM ; colloidal aluminas, such as aluminas, commercially available from Nalco Chemical under the trade name NALCO 8676 ^® ; and colloidal zirconias, such as zirconium oxide, commercially available from Nissan Chemical Company under the trademark HIT-32M ^®.

In some non-limiting embodiments of the present invention, the reinforcing material has a nanostructure. Used in this case, the definition of "nanostructure" refers to a three-dimensional object, where the length of the longest size is in the range from 1 to 1000 nm, for example from 1 to 500 nm, or from 1 to 100 nm, or from 1 to 40 nm.

Nanostructured reinforcing materials can be introduced into the polymer matrix by distributing previously prepared nanostructures, such as, for example, nanoclay, in a polymer solution. Alternatively or additionally, nanostructured reinforcing materials can be introduced into the polymer matrix by forming in situ nanostructures. For example, nanostructured reinforcing materials can be formed in situ by mixing a precursor solution to produce polyurethane or poly (urethane urea) with a precursor for nanostructures to form a mixture, forming nanostructures in the polymer matrix from the nanostructure precursor, and forming the polymer from the polymer precursor solution.

Used in this case, the expression "precursor solution for polyurethane or poly (urethane urea)" refers to any material that can be used as starting material for the formation of polyurethane or poly (urethane urea), as described above. For example, if the desired end product is aliphatic polyurethane, suitable polymer precursors include, but are not limited to, 1,4-butanediol, trimethylolpropane and bis (4-isocyanatocyclohexyl) methane and thiodiethanol.

Used in this case, the expression "precursor for nanostructures" refers to any material that can be used as starting material for the formation of nanostructures.

In some non-limiting embodiments of the invention, a solvent such as water, ethanol, isopropanol, butanol, etc. is added to the mixture.

Nanostructures are formed while the viscosity of the polymer is so low that the nanostructures can themselves be embedded in the polymer matrix. The formation of nanostructures can be initiated using various techniques. In a non-limiting embodiment of the present invention, nanostructures are formed by adjusting the pH of the mixture. An acid or base, such as ammonia, can be used to adjust the pH of the solution. Depending on the corresponding polymer precursor solution and the corresponding precursor for nanostructures, there is an optimal range of pH values in which nanostructures will be formed. One skilled in the art knows that the optimum pH range is determined by both precursors.

In another non-limiting embodiment of the invention, the mixture may be heated to initiate the formation of nanoparticles. The mixture can be heated to any temperature, provided that the mixture is not heated to a temperature above the temperature at which the precursor solution will be destroyed. For example, a precursor solution containing polyurethane or poly (urethane urea) cannot be heated above about 200 ° C, since this temperature corresponds to the temperature at which the polyurethane or poly (urethane urea) begins to decompose. As for the pH range, the optimum temperature range in which particles will form depends on the appropriate solution of the polyurethane or poly (urethane urea) precursor and the corresponding precursor for nanostructures. A person skilled in the art knows that the optimum temperature range is determined by both precursors. Typically, the higher the temperature to which the mixture is heated and / or the longer the mixture is heated, the larger the size of the nanostructures that will be formed.

In another non-limiting embodiment of the invention, the formation of nanostructures is carried out by heating the mixture after setting the pH of the mixture. In another non-limiting embodiment of the invention, the formation of nanostructures is carried out by heating the mixture, and then adjusting the pH of the mixture.

In other various non-limiting embodiments of the invention, nanostructures can be formed by using one or more of the following methods: increasing the pressure on the mixture; a change in the concentration of the precursor solution for polyurethane or poly (urethane urea); the use of an initiator of the formation of nanostructures and nucleation (the addition of not more than 5% of the desired nanostructured material based on the estimated mass of the formed nanostructures, which is well known in the art).

Formed nanostructures are charged samples. If the pH of the solution is adjusted to cause the formation of nanostructures, the charge is the result of pH regulation. If no pH adjustment was performed during the nanostructure formation step, a polymer stabilizer, such as, but not limited to, sodium polymethacrylate in water and ammonium polymethacrylate in water, both of which are commercially available from RT Vanderbilt Company, Inc, can be added to the solution to create a charge. ., Norwalk, CT, such as Darvan ^® 7 and Darvan ^® C respectively.

The third step involves the formation of polyurethane or poly (urethane urea) from a mixture containing a solution of a polyurethane or poly (urethane urea) precursor. The formation of polyurethane or poly (urethane urea) can be caused by using various techniques (as discussed in detail above) based on a solution of a polyurethane or poly (urethane urea) precursor and a precursor for nanostructures.

In another embodiment of the present invention, the second and third stages described above are interchanged.

A method for producing polymers having nanostructures embedded in a polymer matrix in accordance with the present invention is called the in situ process. This means that nanostructures are formed during the same process in which the polymer is formed, in contrast to preformed nanostructures that are dispersed into the polymer solution.

During some methods of the present invention, ions (cations and / or anions) can form in the mixture. The formed ions and other process variables, such as the pressure of the system in which the mixture is held, can affect the final polymer. For example, the amount of nanostructured formation and the morphology of nanostructures will depend on the type and amount of ions present in the solution.

As a rule, nanostructures in a polymer matrix approach each other and collide, since they possess kinetic energy. Under normal conditions, some nanostructures will combine with each other and will form agglomerates due to various interaction forces, for example, due to the van der Waals interaction. As discussed above, agglomeration is not desirable, since nanostructures can actually become particles with the correct size and the desired effect of the introduction of nanostructures is reduced.

However, the methods described above can produce polymers having nanostructures in the polymer matrix that do not form agglomerates to such an extent as to jeopardize the performance of the polymer, for example, to improve the thermal stability of the polymer and / or reduce the reactivity of the polymer. Nanostructures do not form agglomerates, since they are stabilized. Stabilization can be accomplished by electrostatic stabilization and / or steric stabilization.

Since the nanostructures in the polymer matrix are identically charged samples, they repel each other. This prevents the nanostructures from coming so close together that they form an agglomerate. This phenomenon is called electrostatic stabilization.

Since nanostructures are surrounded by a solution of a polymer precursor, when forming a nanostructure, they lose the degree of freedom that they would otherwise have, since the nanostructures are close to each other. This loss of degree of freedom is expressed in thermodynamic terms as a loss of entropy, which creates the necessary barrier to prevent the formation of agglomerates. This phenomenon is called steric stabilization. The same principle applies when the method involves the formation of a polymer before the formation of nanostructures.

The concentration of nanostructures in the polymer matrix can be in the range from 0.1% to 90%, for example from 3% to 85% or from 15% to 80%, based on the total volume. Nanostructures in a polymer matrix can have the following shape: spherical, multifaceted cubic, triangular, pentagonal, rhomboid, needle, rod shape, disk shape, etc. Nanostructures in a polymer matrix can have a ratio of geometric sizes from 1: 1 to 1: 1000, for example, 1: 1 to 1: 100.

Non-limiting examples of suitable nanostructured materials are nanostructures of titanium oxide, alumina, mixed indium and tin oxide (ITO), mixed antimony and tin oxide (ATO), monobutyltin trichloride, indium acetate and antimony trichloride introduced into the polymer matrix. Suitable precursors for titanium oxide nanostructures include, but are not limited to, titanium isopropoxide, titanium (IV) chloride, and potassium titanyloxalate. Suitable precursors for aluminum oxide nanostructures include, but are not limited to, aluminum isopropoxide, tri-tert-butoxide aluminum, tri-sec-butoxide aluminum, triethoxide aluminum and aluminum pentanedione. Suitable precursors for zirconia nanostructures include, but are not limited to, zirconium isopropoxide, zirconium t-butoxide, zirconium butoxide, zirconium ethoxide, zirconium 2,4-pentanedionate, and zirconium trifluoropentanedione.

In a first step, the precursor solution for polyurethane or poly (urethane urea) is mixed with the precursor for nanostructures.

At the second stage, nanostructures are formed in a polymer matrix from a precursor of nanostructures. The formation of nanostructures can be caused by adjusting the pH of the mixture, followed by heating. The pH value can be adjusted by introducing into the mixture an agent, such as ammonia. In the case of ITO nanostructures in an aqueous solution of urethane or urethane urea, the nanostructures begin to form at pH> 8. After establishing the pH, the mixture is heated to a temperature of up to 100 ° C. Heating the solution to a temperature higher than 100 ° C can cause decomposition of the polymer matrix. As discussed above, heating the mixture for a longer period of time can lead to an increase in the size of the nanostructures.

In a third step, the polymer precursor solution is converted to a polymer, as described above, to form polyurethane and poly (urethane urea).

In a non-limiting embodiment of the invention, the obtained reinforced polymer is used as an intermediate layer in laminated glasses for use in automobiles and in architecture. As is known in the art, laminated glass can be produced by applying an intermediate layer between two transparent glass sheets.

In such a specific embodiment of the present invention, as laminated glass for use in automobiles and in architecture, it is important that the nanostructures do not form agglomerates. If the nanostructures form agglomerates and actually reach a diameter of more than 200 nm, the nanostructures will scatter visible light rays to such an extent that transmission through the cushion layer will be insufficient for use. A polymer with nanostructures having an acceptable size for such an application can be detected using a “turbidity value”. The value of turbidity is related to the extent to which there are obstacles to transparency. The larger the nanostructures present in the polymer matrix, the higher the turbidity value. In accordance with the present invention, laminated glass for an automobile and for use in architecture has a haze value of less than or equal to about 1%, for example less than or equal to about 0.3% or less than or equal to about 0.2%, when measured using Hazeguard System (BYK-Gardner, Columbia, MD).

In an embodiment of the invention where a polyurethane or poly (urethane urea) is prepared containing titanium oxide nanostructures embedded in a polymer matrix, the first step may include mixing titanium isopropoxide with a 1-10 wt.% Solution of H ₂ O ₂ and suitable polyurethane or poly (urethane urea) precursors ), which are described above. H ₂ O ₂ acts as an initiator for titanium oxide nanostructures, especially for titanium oxide nanostructures in the octahedral form (in the form of anatase). Optionally, polymers such as polyoxyethylene (20) sorbitan monooleate commercially available as Tween ^® 80 (ICI Ltd., Bridgewater, NJ) , may be added to the solution to help stabilize the titania nanostructures.

At the second stage, titanium oxide nanostructures are formed from the precursor by heating the mixture to a temperature of up to 100 ° C.

In a third step, the polymer precursor solution is converted to polyurethane or poly (urethane urea), as discussed in detail above.

In a non-limiting embodiment of the present invention, a polyurethane or poly (urethane urea) containing nanostructures of titanium oxide, alumina or zirconium oxide embedded in a polymer matrix can be used as an optical lens. A polymer with nanostructures having an acceptable size for an optical lens can be detected using a “haze value”. In accordance with the present invention, an optical lens has a haze value of less than or equal to 0.5%, for example less than or equal to 0.2%, when measured using the Hazeguard System (BYK-Gardner, Columbia, MD).

In a non-limiting embodiment of the invention, a polyurethane having nanostructures of ITO or ATO embedded in a polymer matrix is prepared. Such a polymer can be obtained as follows. In a first step, a solution of the precursor of trimethylolpropane, methylene bis (4-cyclohexylisocyanate) and thiodiethanol is mixed with the precursor of ITO or ATO nanostructures.

A suitable precursor solution for polyurethane is trimethylolpropane, methylene bis (4-cyclohexylisocyanate), thioethanol and includes, but is not limited to, 1,4-butanediol. Suitable precursors for ITO nanostructures include monobutyltin trichloride and indium acetate. A suitable precursor for ATO nanostructures is antimony trichloride.

At the second stage, ITO or ATO nanostructures are formed from the precursor. The formation of nanostructures can be caused by adjusting the pH of the solution by introducing an agent such as ammonia into the mixture, followed by heating the mixture. In the case of ITO nanostructures, nanostructures begin to form at pH> 8. After setting the pH value, the mixture is heated to a temperature of up to 100 ° C. As discussed above, heating the mixture for a longer period of time can lead to an increase in the size of the nanostructures.

In a third step, 1,4-butanediol is mixed with trimethylolpropane, methylene bis (4-cyclohexyl isocyanate), thioethanol, which is well known in the art. For example, 1,4-butanediol, thiodiethanol, trimethylolpropane (TMP) and DESMODUR ^® W can all be mixed in a reactor and heated to 180 ° F. The mixture was mixed in vacuo for approximately 15 minutes and then a tin catalyst, such as dibutyltin dilaurate or bismuth carbonate, was added to the mixture at a concentration of 25 ppm. The mixture is then poured into a glass mold and cured for at least 20 hours at 250 ° F (121 ° C) to form polyurethane.

In a non-limiting embodiment of the invention, trimethylolpropane, methylene bis (4-cyclohexylisocyanate), thiodiethanol having ITO or ATO nanostructures embedded in a polymer matrix are used to obtain an antistatic layer for the windows of an airplane. A polymer with nanostructures has an elastic modulus that is greater than the elastic modulus of standard trimethylolpropane, methylene bis (4-cyclohexyl isocyanate), thioethanol in the absence of ITO / ATO nanostructures.

In other non-limiting embodiments of the invention, the reinforcing material is a nanostructured reinforcing material formed in situ due to swelling of the polyurethane in a solvent containing a precursor for nanostructures, and due to the formation of nanostructures in the polyurethane matrix from the precursor of nanostructures. Non-limiting examples of suitable solvents for mildly swelling the polymer are methanol, propylene glycol methyl ester such as DOWANOL PM (commercially available from Dow Chemical Co., Midland, Michigan), diacetone alcohol, 2-propanol, 1-propanol and acetylpropanol.

A polymer with nanostructures having the appropriate size for use with airplane windows can be detected using a “haze value”. In accordance with the present invention, a multi-layer porthole for aircraft has a haze value of less than or equal to about 1%, for example less than or equal to about 0.5%, when measured using the Hazeguard System (BYK-Gardner).

In some non-limiting embodiments of the present invention, reinforcing materials have a hardness value higher than the hardness of materials that can wear a polymer coating or polymer base by friction. Examples of materials that can wear a polymer coating or polymer base by friction include, but are not limited to, soil, sand, rock, glass, car brushes, etc. The hardness values of particles and materials that can wear a friction polymer coating or polymer base can be determined using a conventional instrumental method for determining hardness, for example, a method for determining Vickers hardness or Brinell hardness; or can be determined by the original Mohs hardness scale, which shows the relative resistance of the material to surface scratching on a scale of one to ten. The Mohs values of several non-limiting examples of particles derived from inorganic materials suitable for use in the present invention are shown in Table A below.

Table a Particle material Mohs hardness (original scale) Boron nitride 2 ¹ Graphite 0.5-1 ² Molybdenum disulfide 1 ³ Talc 1-1.5 ⁴ Mica 2.8-3.2 ⁵ Kaolinite 2.0-2.5 ⁶ Gypsum 1.6-2 ⁷ Calcite (Calcium Carbonate) 3 ⁸ Calcium fluoride 4 ⁹ Zinc oxide 4,5 ¹⁰ Aluminum 2.5 ¹¹ Copper 2.5-3 ¹² Iron 4-5 ¹³ Gold 2.5-3 ¹⁴ Nickel 5 ¹⁵ Palladium 4.8 ¹⁶ Platinum 4.3 ¹⁷ Silver 2.5-4 ¹⁸ Zinc sulphide 3,5-4 ¹⁹

¹ K. Ludema, Friction. Wear Lubrication (1996), p. 27, incorporated herein by reference.

² R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (1975), p. F-22.

³ R. Lewis, Sr., Hawlev's Condensed Chemical Dictionary, (12th Ed. 1993), p. 793, incorporated herein by reference.

⁴ Hawley's Condensed Chemical Dictionary (12th Ed. 1993), p. 1113, incorporated herein by reference.

⁵ Hawley's Condensed Chemical Dictionary (12th Ed. 1993), p. 784, incorporated herein by reference.

⁶ Handbook of Chemistry and Physics , p. F-22.

⁷ Handbook of Chemistry and Physics , p. F-22.

⁸ Friction, Wear, Lubrication , p. 27.

⁹ Friction, Wear, Lubrication , p. 27.

¹⁰ Friction, Wear, Lubrication , p. 27.

¹¹ Friction, Wear, Lubrication , p. 27.

¹² Handbook of Chemistry and Physics , p. F-22.

¹³ Handbook of Chemistry and Physics , p. F-22.

¹⁴ Handbook of Chemistry and Physics , p. F-22.

¹⁵ Handbook of Chemistry and Physics , p. F-22.

¹⁶ Handbook of Chemistry and Physics , p. F-22.

¹⁷ Handbook of Chemistry and Physics , p. F-22.

¹⁸ Handbook of Chemistry and Physics , p. F-22.

¹⁹ R. Weast (Ed.), Handbook of Chemistry Physics, CRC Press (71.sup.st Ed. 1990), pp. 4-158.

In some non-limiting embodiments, the reinforcing material may be formed from a primary material that is coated, clad, or encapsulated with one or more secondary materials to form a composite material that has a harder surface. In other non-limiting embodiments, the implementation of the particles of the amplifier can be obtained from the primary material, which is coated, clad or encapsulated using various forms of the primary material with the formation of a composite material that has a harder surface.

In some non-limiting examples, inorganic particles obtained from an inorganic material, such as silicon carbide or aluminum nitride, can be obtained by coating from silicon dioxide, carbonate or nanoclay to form a useful composite particle. In other non-limiting embodiments, a silane coupling agent with alkyl side chains may interact with the surface of an inorganic particle formed from an inorganic oxide to produce a useful composite particle having a softer surface. Other examples include cladding, encapsulating particles, or coating particles that are formed from non-polymeric or polymeric materials using various non-polymeric or polymeric materials. One non-organizing example of such composite particles is DUALITE ^™ , which is a calcium carbonate coated polymer particle, and these composite particles are commercially available from Pierce and Stevens Corporation of Buffalo, NY

In some non-limiting embodiments, the particles are formed from solid lubricants. Used in this case, the definition of “solid lubricant” means any solid substance used between two surfaces to provide protection against damage during relative movement and / or to reduce friction and abrasion. In some non-limiting embodiments of the invention, solid lubricants are inorganic solid lubricants. Used in this case, the definition of “inorganic solid lubricant” means that solid lubricants have a characteristic crystalline behavior, which forces them to separate into thin, flat plates that slide easily one on top of the other and therefore produce an antifriction lubricating effect (see R Lewis, Sr. Hawley's Condensed Chemical Dictionary (12th Ed. 1993), p. 712, which is incorporated herein by reference). Friction is the sliding resistance of one solid material over another, F. Clauss. Solid Lubricants and Self-Lubricating Solids (1972), p. 1, which is incorporated herein by reference.

In some non-limiting embodiments of the invention, the particles have a scaly structure. Particles having a scaly structure are composed of layers or plates of atoms in a hexagonal arrangement with strong binding within the formation and weak van der Waals binding between the layers, which provides low shear strength between the layers. A non-limiting example of a scaly structure is a hexagonal crystal structure. Inorganic solid particles having a scaly structure of fullerene (i.e. buckyball) can also be used.

Non-limiting examples of suitable flaky materials that can be used to make particles of the present invention are boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixtures of any of the above . Suitable metal dichalcogenides include molybdenum disulphide, molybdenum disulide, tantalum disulphide, tantalum disulide, tungsten disulphide, tungsten diselide, as well as mixtures of any of these compounds.

In some non-limiting embodiments of the invention, the reinforcing material may be strands of fiberglass. Fiberglass strands are obtained from primary glass fibers, a class of filaments, as is generally recognized, based on oxide compositions, such as silicates, selectively modified with other oxide and non-oxide compositions. Useful primary glass filaments can be obtained from any type of fiberable glass composition known to one skilled in the art and include filaments made from fiberable glass compositions such as E-glass, A-glass, “C-glass”, “D-glass”, “R-glass”, “S-glass” and derivatives of “E-glass” which do not contain fluorine and / or boron. Used in this case, the definition of "capable of forming fiber" means a material that can be formed, as a rule, into a continuous filament, fiber, strand or yarn. Used in this case, the definition of "derivative of E-glass" means a glass composition that includes small amounts of fluorine and / or boron or may not contain fluorine and / or boron. In addition, the definition used in this case, "minor amounts of fluorine" means less than 0.5 wt.% Fluorine or less than 0.1 wt.% Fluorine, and the definition of "minor amounts of boron" means less than 5 wt.% Boron or less than 2 wt.% boron. Basalt and mineral wool are examples of other fiber-forming glass materials that can be used in the present invention. Non-limiting examples of suitable inorganic glass fiber incapable materials are ceramic materials such as silicon carbide, carbon black, quartz, graphite, mullite, alumina, and piezoelectric ceramic materials. In some non-limiting embodiments of the invention, glass primary filaments are made from E-glass. These compositions and methods for making primary glass filaments from them are well known to those skilled in the art, and such glass compositions and fiber forming methods are discussed by K. Loewenstein. The Manufacturing Technology of Continuous Glass Fiber , (3d Ed. 1993), pp. 30-44, 47-60, 115-122, 126-135, which is incorporated herein by reference.

Glass fibers may have a nominal filament diameter in the range of from about 5.0 to about 30.0 μm (corresponding to the designation of the filament from D to Y). Typically, fiberglass strands have a strand-coating composition that is compatible with a composition deposited on at least a portion of the surfaces of the fiberglass strands, such as a substantially dried residue. Reinforcing materials from fiberglass strands can be used in chopped form, in the form of generally continuous strands, mats, etc.

Particles can also be hollow particles formed from materials selected from polymer and non-polymer inorganic materials, polymer and non-polymer organic materials, composite materials, and mixtures of any of these materials. Non-limiting examples of suitable materials from which hollow particles can be obtained are discussed above. In some embodiments, the hollow particles may be hollow glass spheres.

In some non-limiting embodiments, the implementation of reinforcing materials can be obtained from non-polymer organic materials. Non-limiting examples of non-polymeric organic materials that can be used in the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), diamond, carbon black and stearic acid amide.

In some non-limiting embodiments, the implementation of the particles can be obtained from inorganic polymeric materials. Non-limiting examples of useful inorganic polymeric materials are polyphosphazenes, polysilanes, polysiloxanes, polygermans, polymer sulfur, polymer selenium, silicones, and mixtures of any of these materials. A non-limiting example of a particle derived from an inorganic polymer material that is suitable for use in the present invention is TOSPEARL (see RJ Perry. “Applications for Cross-Linked Siloxane Particles”, Chemtech . February 1999, pp. 39-44), which represents is a particle derived from crosslinked siloxanes, and which is commercially available from Toshiba Silicones Company, Ltd., Japan.

Particles can be obtained from synthetic, organic, polymeric materials that are chemically different from polyurethane or poly (urethane urea). Non-limiting examples of suitable organic polymeric materials include, but are not limited to, thermoset materials and thermoplastic materials. Non-limiting examples of suitable thermoplastic materials are thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polycarbonates, polyolefins such as polyethylene, polypropylene and polyisobutene, acrylic polymers such as styrene and acrylic acid copolymers, and polymers containing polyacrylates polyurethanes, vinyl polymers and mixtures of any of the listed materials.

In some non-limiting embodiments, the polymeric organic material is a (meth) acrylic polymer or copolymer containing at least one functional group selected from the group consisting of silane groups, carboxyl groups, hydroxyl groups and amide groups. In some non-limiting embodiments, the implementation of such (meth) acrylic polymers or copolymers may be present in the form of nanofibers having a diameter of up to about 5000 nm, for example from about 5 to about 5000 nm, or having a diameter less than the wavelength of visible light, for example 700 nm or less, for example from about 50 to about 700 nm. The fibers can be in the form of a tape, and in this case, the diameter, as implied, means the largest fiber size. Typically, the width of the ribbon-like fibers can be up to about 5000 nm, for example from about 500 to about 5000 nm, and the thickness is up to about 200 nm, for example from about 5 to about 200 nm. Fibers can be obtained by electroforming a ceramic melt, polymer melt or polymer solution.

Suitable (meth) acrylic polymers can be obtained by polymerization by addition of unsaturated polymerizable materials that contain silane groups, carboxyl groups, hydroxyl groups and amine or amide groups. Non-limiting examples of useful silane groups are groups that have a Si-X _n structure (where n is an integer ranging from 1 to 3, and X is selected from a chlorine atom, alkoxy esters and / or acyloxy esters). Such groups are hydrolyzed in the presence of water, including air moisture, to form silanol groups, which condense to form —Si — O — Si— groups. The (meth) acrylic polymer may contain hydroxyl functionality, for example, when using an ethylenically unsaturated polymerizable monomer with hydroxyl functionality, such as hydroxyalkyl esters of (meth) acrylic acids containing from 2 to 4 carbon atoms in the hydroxyalkyl group. The (meth) acrylic polymer optionally contains nitrogen functionality introduced from nitrogen-containing ethylenically unsaturated monomers such as amines, amides, ureas, imidazoles and pyrrolidones. Additional information on such (meth) acrylic polymers and fiber forming methods is provided in US Pat. No. --- / ------ under the name "Transparent Composite Articles" and in US Patent Application Reg. No. --- / ------ under the name "Organic-Inorganic Polymer Composites and Their Preparation by Liquid Infusion", each of which is under consideration and is included here as a reference.

Non-limiting examples of suitable fiber-forming organic materials are cotton, cellulose, natural rubber, linen, ramie, hemp, sisal and wool. Non-limiting examples of suitable fiber-forming organic polymeric materials are materials derived from polyamides (such as nylon and aramid) (such as KEVLAR ^™ aramid fibers), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylic polymers (such as polyacrylonitriles), polyolefins, polyurethanes, and vinyl polymers (such as polyvinyl alcohol). Non-glass fiber-forming materials that can be used in the present invention, and methods for producing and processing such fibers are discussed in detail in Encyclopedia of Polymer Science and Technology , Vol. 6 (1967), pp. 505-712, which is expressly incorporated herein by reference.

It is understood that mixtures or copolymers of any of the above materials and combinations of fibers formed from any of the materials listed above can be used in the present invention, if desired. Moreover, the definition of "strand" may include at least two different fibers made from different fiber-forming materials. Used in this case, the definition of "fiber-forming" means a material capable of forming, as a rule, in a continuous filament, fiber, strand or yarn.

Suitable thermoplastic fibers can be formed using a variety of polymer extrusion methods and fiber spinning methods, such as, for example, drawing, melt spinning, dry spinning, wet spinning and air gap spinning. Such methods are well known to specialists in this field of technology and their further discussion is not considered to be necessary in this description. If further information is needed, such methods are discussed in Encyclopedia of Polymer Science and Technology , Vol. 6 (1967), pp. 507-508.

Non-limiting examples of useful polyamide fibers are nylon fibers such as nylon 6 (caprolactam polymer), nylon 6.6 (a condensation product of adipic acid and hexamethylene diamine), nylon 12 (which can be obtained from butadiene) and nylon 10, polyhexamethylene adipamide, aramid polyamide imides such as KEVLAR ^™ , which is commercially available from EI DuPont de Nemours, Inc., Wilmington, Del.

Non-limiting examples of useful thermoplastic polyester fibers are fibers consisting of polyethylene terephthalate and polybutylene terephthalate.

Non-limiting examples of useful fibers formed from acrylic polymers are polyacrylonitriles having at least about 35 wt.% Acrylonitrile units or at least about 85 wt.% That can be copolymerized with other vinyl monomers, such as vinyl acetate , vinyl chloride, styrene, vinyl pyridine, acrylic esters or acrylamide (see Encyclopedia of Polymer Science and Technology , Vol. 6, pp. 559-561).

Non-limiting examples of useful polyolefin fibers typically consist of at least about 85% by weight of ethylene, propylene or other olefins (see Encyclopedia of Polymer Science and Technology , Vol. 6, pp. 561-564).

Non-limiting examples of useful fibers formed from vinyl polymers can be prepared from polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene and polyvinyl alcohol.

Other non-limiting examples of thermoplastic fiber-forming materials that are believed to be useful in the present invention are fiber-forming polyimides, polyethersulfones, polyphenylsulfones, polyetroketones, polyphenylene oxides, polyphenylene sulfides and polyacetals.

It is understood that mixtures or copolymers of any of the above materials and combinations of fibers obtained from any of the above materials can be used in the present invention, if desired. In addition, thermoplastic fibers can have an antistatic coating applied to them.

Suitable reinforcing materials include mats or fabrics consisting of any of the fibers described above. An increasingly popular process for forming composites is injection molding or stamping of a sheet-forming thermoplastic resin reinforced with fibers such as glass mat, often called thermoplastics, glass reinforced or “GMT”. Such composite sheets can be used to obtain products such as automotive parts and computer cases. An example of a commercially successful GMT sheet is the AZDEL ^® moldable composite sheet, which is obtained by extruding layers of a sheet of polypropylene resin with needle mats from a continuous strand of fiberglass. AZDEL ^® Composite Sheet is commercially available from Azdel, Inc., Shelby, NC

For hardening the resin matrix, US Pat. Nos. 3,664,909, 3,713,962 and 3,850,723 disclose fiber mats of non-woven filaments that can be interlaced with reinforcing mats of fiber strands.

US Pat. No. 4,847,740 discloses an insulating medium formed by stitching a loosened layer of inorganic fibers, such as fiberglass, bonded together by a carrier web, which is a mixture of inorganic and organic fibers, the carrier web containing up to about 10 wt.% Organic fibers.

US Patent Nos. 4,948,661, 5,011,737, 5,071,608 and 5,098,624 disclose fiber-reinforced thermoplastic molded products made by carefully mixing reinforcing glass fibers and thermoplastic fibers into a fabric and heating the fabric to the melting temperature of thermoplastic fibers by applying pressure to the fabric to press the fabric against the combined structure .

A non-limiting example of a useful polypropylene fiber nonwoven mat is a commercially available product from Fiberweb N.A., Inc. Simponville, S.C.

Non-limiting examples of suitable thermosetting reinforcing materials are thermosetting polyesters, vinyl esters, epoxies, phenolic resins, aminos, thermosetting polyurethanes, and mixtures of any of these materials. A specific non-limiting example of a synthetic polymer particle derived from an epoxy material is an epoxy microgel particle.

The concentration of enhancer particles present in the cured article or coating can be determined, if necessary, using various analytical techniques well known in the art, such as transmission electron microscopy (TEM), surface scanning electron microscopy (X-SEM) , atomic force microscopy (AFM) and X-ray spectroscopy.

In some non-limiting embodiments, the present invention relates to cured compositions as previously described, wherein the enhancer particles have an average particle size of less than about 100 microns before being introduced into the composition or less than about 50 microns before being introduced into the composition. In other non-limiting embodiments, the present invention relates to the cured compositions described above, wherein the enhancer particles have an average particle size that is in the range of from about 1 to less than about 1000 nm before being introduced into the composition, or from about 1 to about 100 nm before being introduced. into the composition.

In other non-limiting embodiments, the present invention relates to cured compositions as previously described, wherein the particles have an average particle size in the range of from about 5 to about 50 nm before being introduced into the composition, or from about 5 to about 25 nm before being introduced into the composition.

In an embodiment where the average particle size is at least about one micron, the average particle size can be measured in accordance with known laser scattering techniques. For example, the average particle size of such particles is measured using a Horiba Model LA 900 particle size laser diffraction apparatus that uses a 633 nm helium-neon laser to measure particle size and assume that the particles are spherical; that is, “particle size” refers to the smallest sphere that will completely encompass the particle.

In an embodiment of the present invention, where the particle size is less than or equal to one micron, the average particle size can be determined by visually evaluating the electron micrograph image in a transmission electron microscope (TEM) by measuring the particle diameter in the image and calculating the average particle size based on the increase TEM image. An ordinary person skilled in the art will understand how to obtain such a TEM image, and a description of one such method is disclosed in the examples below. In one non-limiting embodiment of the present invention, a TEM image is obtained with a 105,000-fold increase, and a conversion coefficient is obtained by dividing the increase by 1000. In a visual assessment, the particle diameter is measured in millimeters, and the measurement result is converted to nanometers using a conversion coefficient. The particle diameter refers to the smallest diameter of the sphere that will completely surround the particle.

The shape (or morphology) of the reinforcing material may vary depending on the particular embodiment of the present invention and its intended use. For example, spherical morphology (such as solid beads, microbeads or hollow spheres), as well as particles that are cubic, flat or needle-like (elongated or fibrous) can usually be used. In addition, the particles can have an internal structure, which can be hollow, porous, solid, or a combination of any of the above, for example, a hollow center with porous or solid walls. For further information on the characteristics of suitable particles, see H. Katz et al. (Ed.), Handbook of Fillers and Plastics (1987), pp. 9-10, which is incorporated herein by reference.

One skilled in the art will recognize that mixtures of one or more particles having different average particle sizes can be incorporated into compositions of the present invention to impart desired properties and characteristics to the composition. For example, particles of varying sizes may be used in the compositions of the present invention.

In some non-limiting embodiments of the invention, the reinforcing material (s) are present in the composition in an amount in the range of from about 0.01 to about 75 wt.% Or from about 25 to about 50 wt.% Based on the total weight the components that make up the composition.

Enhancer particles may be present in the dispersion, suspension or emulsion in the carrier. Non-limiting examples of suitable carriers include, but are not limited to, water, solvents, surfactants, or mixtures of any of the above materials. Non-limiting examples of suitable solvents include, but are not limited to, mineral oil, alcohols such as methanol or butanol, ketones such as methylamyl ketone, aromatic hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl ether, esters, aliphatic compounds and mixtures of any of the above substances.

Dispersion techniques may be used, such as grinding, grinding, microfluidization, sonication, or any other dispersion technique well known in the art of coating formulations or molded products. On the other hand, the particles can be dispersed using any other dispersion techniques known in the art. If desired, particles in a form other than the colloidal form can be added to the mixture of other components of the composition later and dispersed therein using any dispersion techniques known in the art.

Another embodiment of the present invention relates to coated automotive backings consisting of an automotive backing and a cured composition applied to at least a portion of an automotive backing, where the cured composition is selected from any of the above compositions. In yet another embodiment, the present invention relates to a method for producing a coated automotive backing, which comprises creating an automotive backing and applying at least a portion of the automotive backing to a coating composition selected from any of the above compositions. Again, the components used to form the cured composition can be selected from the above components, and additional components can also be selected from the above additional components.

Suitable flexible elastomeric bases can be any thermoplastic or thermosetting synthetic materials well known in the art. Non-limiting examples of materials for a suitable flexible elastomeric base are polyethylene, polypropylene, thermoplastic polyolefin (TPO), injection molded polyurethane (RIM), and thermoplastic polyurethane (TPU).

Non-limiting examples of thermosetting materials that can be used as bases for coating the compositions of the present invention are polyesters, epoxides, phenolic resins, polyurethanes such as RIM thermosetting materials, and mixtures of any of the above materials. Non-limiting examples of suitable thermoplastic materials are thermoplastic polyolefins such as polyethylene, polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, acrylonitrile butadiene-styrene (ABS) copolymers-ethylene-ethylene-ethylene-propylene diene terpolymer (EPDM), copolymers and mixtures of any of the above examples.

Non-limiting examples of acceptable metal bases that can be used as bases for coating of the compositions of the present invention are iron-containing metals (e.g., iron, steel and its alloys), non-iron-containing metals (e.g., aluminum, zinc, magnesium and their alloys ), as well as mixtures of any of the above materials. In a specific application for automotive parts, the base can be obtained from cold rolled steel, galvanized steel, such as hot dipped galvanized steel, galvanized steel, aluminum and magnesium.

When the bases are used as parts for the manufacture of vehicles (including, but not limited to, cars, trucks and tractors), they can be of any shape and can be selected from the metal and flexible bases described above. Typical forms of car body parts can be carcasses (frames), hoods, doors, fenders, mirror stands, bumpers and metal trim for vehicles.

In embodiments of the present invention that relate to automotive applications, the cured compositions can be, for example, an electrodepositable coating, a primer coating, a basecoat and / or a topcoat. Suitable top fixing coatings are single component coatings and composites (base coat) / transparent layer. One-component coatings are obtained from one or more layers of a colored coating composition.

In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of Groups AP can be reinforced with fiberglass to produce a composite product such as, for example, a propeller blade, explosion-proof panels, bulletproof panels, and fairings.

R group

In some non-limiting embodiments, polyurethanes and poly (urethaneureas) of Groups A-Q may be used as one or more layers in a multilayer product. If desired, the multilayer product may be laminated.

In some non-limiting embodiments, the polymer is cut while it is warm, granulated, extruded and / or crushed and calendared into sheets, assembled into laminates and incubated for several days, weeks or for a longer period at room temperature (approximately 25 ° C) .

In some non-limiting embodiments, the present invention provides articles having multiple layers of polyurethanes and / or poly (urethane ureas) of the present invention. The thickness of each layer and the total thickness of the product may vary, if necessary. Non-limiting examples of acceptable layer thicknesses and products are given below. Layers can be laminated together, if desired.

In some non-limiting embodiments, the present invention provides multilayer articles or laminates comprising: (a) at least one layer of polyurethane (s) or poly (urethane urea) (i) of the present invention described above; and (b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, stone, fabric, metal or organic polymeric material and combinations thereof. In some non-limiting embodiments of the invention, the layer (a) of the polyurethane (s) or poly (urethane urea) (i) of the present invention is chemically or physically different from the organic polymer material of the layer (b), that is, it has at least one other atom, an arrangement atoms or configuration. In other embodiments, two or more layers of the same (s) or similar (s) polyurethane (s) or poly (urethane urea) (in) of the present invention can be used.

In certain nonlimiting embodiments, the substrate is an optically clear polymerized organic material prepared from a thermoplastic polycarbonate resin, such as the carbonate-linked resin derived from bisphenol A and phosgene, which is sold under the trade name ^{LEXAN ® (GE Plastics of Pittsfield,} Massachusetts); polyester, such as material sold under the trade name MYLAR (EI DuPont de Nemours Co., Wilmington, Delaware); poly (methyl methacrylate), such as material sold under the trade name PLEXIGLAS (Altuglas International of Philadelphia, Pennsylvania); polyhexylene polycarbonate-based polyurethanes; polymers of a polyol (allyl carbonate) monomer, in particular diethylene glycol bis (allyl carbonate), and this monomer is sold under the trade name CR-39 (PPG Industries, Inc.), and polymers of copolymers of a polyol (allyl carbonate), for example diethylene glycol bis (allyl carbonate), with other copolymerizable monomer materials, such as copolymers with vinyl acetate and copolymers with polyurethane having terminal diacrylate functionality, which are described in US patent No. 4360653 and 4994208; and copolymers with aliphatic urethanes, the end of which contains allyl or acryl functional groups, which are described in US patent No. 5200483; poly (vinyl acetate), polyvinyl butyral, polyurethane, polymers of a member of the group including diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers and ethoxylated trimethylolpropane triacetate monomers; cellulose acetates, cellulose propionates, cellulose butyrates, cellulose acetate butyrates, polystyrenes and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.

A non-limiting example of a suitable polyhexylene polycarbonate-based polyurethane can be prepared as follows: a prepolymer with hydroxyl functionality of 0.2 equivalents of carbonate diol based on hexanediol with a molecular weight of 1000 (PC-1733, commercially available from Stahl), 0.8 equivalents of 1, 5-pentadiol and 1.0 equivalent of trimethylhexanediisocyanate. The components are heated to 180 ° F. (82 ° C.) and 100 ppm dibutyltin dilaurate is used as a catalyst. The prepolymer has an equivalent weight of 218 g / equivalent. The hydroxyl-terminated trimeric prepolymer is dissolved in a solvent, cyclohexanone, 1 equivalent of Desmodur 3390 (triisocyanurate hexanediisocyanate trimer) is added as a crosslinking agent and mixed. The coating solution contains 95% solids with a viscosity of 3000 centipoise. The solution can be sprayed onto any bisphenol A polycarbonate such as Lexan and oven cured at 250 ° F (212 ° C) for 4 hours. The coating thickness may be in the range of 2 to 5 mils, and the coating is elastomeric.

The number and thickness of the layers may vary, if desired. For example, the thickness of one layer may be in the range of from about 0.1 mm to about 60 cm, or from about 2 mm to about 60 cm, or from about 0.3 to about 2.5 cm. The number of layers can be in the range of 2 to 10 or 2 to 4, if necessary. The total thickness of the multilayer product or laminate may range from about 2 mm to about 15 cm or more, or from about 2 mm to about 5 cm. In the case of ballistic applications, the total thickness of the polyurethane or poly (urethane urea) of the present invention can be in the range from about 2 mm to about 15 cm or more, or from about 2 mm to about 5 cm. In addition, in the case of ballistic applications, suitable bases for layering polyurethane (s) and / or oli (uretanmocheviny) (yn) of the present invention are, for example, polyesters, polycarbonates or polyether thermoplastic elastomers. The layer (s) of the polyurethane or poly (urethane urea) of the present invention can be located (s) on the outside of the laminate (towards potential ballistic impact), on the inside of the laminate, or somewhere else in between.

Groups A-R

In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention may have hard segments from about 10 to about 100 wt.%, Or from about 20 to about 80 wt.%, Or from about 30 to about 75 wt.%. The calculation of hard segments is discussed in detail above.

In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention typically have a urethane (Wu) content of from about 20 to about 40 wt.%, Or from about 21 to about 36 wt.%, Or from about 30 to about 40 wt.%. The urethane content is the mass percentage of urethane bridges present in the polymer, and can be calculated by determining the total number of equivalents and from it the total mass of all reagents and dividing the total mass of urethane bridges that can be obtained from these reagents by the total mass of the reagents themselves. The following example further explains this calculation. In Example I, Formulation 1, which is described below, of a polyurethane product according to the present invention, is obtained by reacting 0.7 equivalents of 1,4-butadiol, 0.3 equivalents of trimethylopropane and one equivalent of 4,4'-methylene bis (cyclohexyl isocyanate) ( DESMODUR W). The equivalent mass of 1,4-butanediol is 45, the equivalent mass of trimethylolpropane is 44.7 (corrected for impurities), and the equivalent mass of DESMODUR W is 131.2. Therefore, the actual weight of the ingredients used is 31.54 parts by weight. 1,4-butanediol, 13.2 parts by weight trimethylolpropane and 131.2 parts by weight DESMODUR W, or the total mass of reagents 175.9 wt.h. One equivalent of DESMODUR W will produce one equivalent of urethane bridges. The equivalent mass of the urethane bridge is 59, so the total mass of the urethane bridges, determined by multiplying the equivalent mass by the number of equivalents, will also be 59. Therefore, the total mass of the urethane bridges, 59, divided by the total mass of the reagents, 175.9, multiplied by 100, so that translate into percentages, will give a mass percentage of urethane bridges 33.49 wt.%.

Similarly, the mass percentage of cyclic structures (W _c ) (such as, for example, cyclohexyl) can be calculated. In Example I, Formulation 1, the only material giving cyclohexyl residues is DESMODUR W. One equivalent of DESMODUR W will give one equivalent of cyclohexyl residue, which has an equivalent weight of 81. Therefore, the total mass of cyclohexyl residues will be 81, and this value divided by on the total mass of reagents or 175.9, will give W _c 46%. In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention may have a cyclic group content of from about 10 to about 80 wt.%, From about 20 to about 70 wt.%, From about 30 to about 70 wt.%, Or from about 30 to about 60 wt.%.

In some non-limiting embodiments, the resulting polyurethanes and poly (urethane ureas) of the present invention can be solid and substantially transparent upon curing. In some non-limiting embodiments, the polyurethane can be partially cured or completely cured so that essentially the following reactions do not proceed.

In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention typically have a number average molecular weight, which is estimated from measurements of intrinsic viscosity of at least about 20,000 g / mol, or it is in the range of from about 20,000 to about 1,000,000 g / mol or in the range of from about 20,000 to about 800,000 g / mol. The polyurethanes and poly (urethane ureas) of the present invention typically have an average molecular weight based on crosslinking of at least about 500 g / mol, in some embodiments, in the range of from about 500 to about 15,000 g / mol or in the range of about 1800 up to about 15000 g / mol. The polyurethanes and poly (urethane ureas) of the present invention typically have a crosslink density of at least about 11000 g / mol.

In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention may have a low density upon curing. In some non-limiting embodiments, the density may be at least 0.9 to less than 1.25 g / cm ³ , or at least 1.0 to less than 1.45 g / cm ³ , or 1.08 to less than 1.37 g / cm ³ , or from 1.08 to 1.13. In some non-limiting embodiments of the invention, the density of the polyurethanes and poly (urethane ureas) of the present invention may be lower than that of LEXAN (density is approximately 1.21 g / cm ³ ) and conventional stretched acrylic polymer (density is approximately 1.18 g / cm ³ ) Density can be measured using a DensiTECH device manufactured by Tech Pro, Incorporated. In non-limiting embodiments, the density is measured in accordance with ASTM-D 792-00.

In addition, some optically pure polyurethanes and poly (urethane ureas) show a low-temperature exotherm at approximately

-70 ° C (differential thermal analysis can be performed using a DuPont 900 thermal analyzer) and at approximately 11 ° C, indicating that the polymers are usually amorphous.

In some non-limiting embodiments of the invention, when measured in a nitrogen atmosphere, softening temperatures from about 65 ° C to about 200 ° C, melting points from about 80 ° C to about 220 ° C, and decomposition temperatures from about 280 ° C to about 330 ° C are typical .

The polyurethanes and poly (urethane ureas) of the present invention can be used to obtain products having good resistance to impact loads or flexibility, high impact strength, high tensile strength, resistance to deformation due to thermal heating, good hardness, high Young's modulus, high K coefficient, good solvent resistance, high purity or transparency, high light transmission, low turbidity, good weathering resistance, good m energy absorption, good resistance to moisture, good resistance to ultraviolet light and / or good ballistic resistance.

Non-limiting examples of suitable methods and equipment for measuring impact resistance and toughness are discussed in detail above.

In some embodiments of the invention, the deformation temperature due to thermal heating of the cured products of the present invention may be at least about 190 ° F (88 ° C) or about 200 ° F (93 ° C) as determined in accordance with ASTM-D 648.

The hardness of polyurethanes and poly (urethane ureas) can be determined using Shore hardness, and accordingly, in some embodiments, the products of the present invention have Shore D hardness at room temperature (25 ° C.) using a Shore D hardness tester of at least about 75 or at least about 80.

The tensile strength at yield or at break can be measured in accordance with ASTM-D 638-03. In some non-limiting embodiments, the yield strength is at least about 6,800 psi according to ASTM-D 638-03, or from about 6,800 psi to about 20,000 psi. square inch (from about 47 to about 138 MPa), or from about 12,000 psi to about 20,000 psi (from about 83 to about 138 MPa).

Young's modulus can be measured in accordance with ASTM-D 638-03. In some non-limiting embodiments, the Young's modulus is at least about 215,000 psi (about 1,482 MPa), or from about 215,000 psi (about 1,482 MPa) to about 600,000 psi (about 4137 MPa), or from about 350,000 psi (about 2,413 MPa) to about 600,000 psi (about 4,137 MPa). For the cockpit windows of commercial aircraft, when the cockpit pressure is 10 psi (0.07 MPa) or much more than the external pressure, the cockpit windows can bend toward air flow, which leads to an increase in noise and lower fuel efficiency. Higher values of Young's modulus indicate increased stiffness and a lower tendency to bend the porthole towards air flow. In some non-limiting applications for airplane windows, Young's modulus values may be at least about 350,000 (about 2,413 MPa). In typical ballistic applications, the outer layers are glass that is hard enough to deform the bullet due to stress distribution when it strikes over a large area before it passes through the layers below. Poly (urethane urea) obtained in accordance with example A, formulation 125, in accordance with the present invention, having a thickness of approximately 0.125 inches (0.3 cm), flattens a 9 mm bullet fired at 1350 ft / s (411 m / s) from a distance of 20 feet (6.1 m). Although the layer collapses into 2 cracked areas, it does not shatter in a large area like glass, which will provide higher visibility for the passenger to avoid attacking the vehicle.

The K coefficient is a measure of crack propagation. Crack propagation can be measured in accordance with US Dept. of Defense MIL-PRF-25690B (January 29, 1993). In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention have a crack propagation coefficient K of at least about 1000 lb / in ^3/2 (1098800 N / m ^3/2 ), or from about 1000 lb / in ^{3 / 2} (1098800 N / m ^3/2 ) to about 4000 lb / in ^3/2 (4395200 N / m ^3/2 ), or from about 2000 lb / in ^3/2 (2197600 N / m ^3/2 ) to about 4,000 psi ^3/2 (4,395,200 N / m ^3/2 ).

Compositions suitable for use in car windshields meet standard minimum transmittance requirements of 70%, or 86.5%, or higher (light source A, 2840 K tungsten light bulb) or less than 2% turbidity (ANSI. CODE Z-26.1 , 1966, Test No. 18). The percent light transmission and percent turbidity can be measured using a Hunter Pivotable Sphere Haze Meter turbidimeter in accordance with ASTM E903-82.

The polyurethanes and poly (urethane ureas) of the present invention may have outstanding weather tolerance characteristics, measured by resistance to ultraviolet light and hydrolytic stability. Exposure using Fade-O-Meter ^® can be carried out in accordance with ASTM-G 25-70, Method A, using Fade-O-Meter, Type FDA-R, Serial No. F02951, manufactured by Atlas Electric Devices Co., Chicago, Illinois. The light source may be an arc lamp with carbon electrodes, enclosed in a spherical casing made of quartz glass. The operating temperature of the Fade-O-Meter (black panel) can be 140 ° F (60 ° C), and the unit operates in the absence of water in the spray assembly. The dimensions of the sample are 21/2 × 1/8 inch (6.35 × 15.24 × 0.32 cm). Exposure using Weather-O-Meter ^® may be conducted in accordance with ASTM-D 1499-64 standard using Weather-O-Meter, DMC type, serial № WO-1305. The type of light source is an arc lamp with a double carbon electrode, enclosed in a spherical casing made of quartz glass. The operating temperature of the black panel can be 140 ° F (60 ° C). Deionized water is sprayed at a temperature of approximately 70 ° F (21 ° C). The number and type of nozzles used for spraying water correspond to four No. 50 nozzles. On the other hand, UV resistance can be determined using the QUV test for 1000 hours in accordance with ASTM-G 53.

Abrasion resistance can be measured using a Taber abrasive machine that has a 500 g CS-10F abrasive wheel for a 3 × 3 × 1/8 inch (7.62 × 7.62 × 0.32 cm) specimen according to ASTM -D 1044-99. In some non-limiting embodiments, performing 100 cycles on a Taber abrasive machine can result in 30% turbidity of the elongated acrylic polymer and in a turbidity of 5% to 40%, or 10% to 15%, or less than 5% for polyurethanes and poly (urethane ureas) of the present invention.

The polyurethanes and poly (urethane ureas) of the present invention can have good resistance to hairline cracking by solvents and acids. Hair crack resistance can be measured in accordance with U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993). Non-limiting examples of solvents and acids for testing stress cracking are methanol, isopropanol, ethylene glycol, propylene glycol, ethyl acetate, acetone, toluene, isopropyl acetate, Skydrol (hydraulic fluid), jet fuel such as JP-4, and 75% aqueous solution of sulfuric acid. In some non-limiting embodiments, uncoated articles made from the polyurethanes and poly (urethane ureas) of the present invention are resistant to hairline cracking under stress in an organic solvent and 75% aqueous sulfuric acid solution of at least about 1000 psi. inch (6.9 MPa) of tensile stress, or from about 1,000 psi (6.9 MPa) to about 4,000 psi (27.6 MPa), or from about 2,000 psi ( 13.8 MPa) to approximately 4000 psi (27.6 MPa). In some non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention, when not coated, can withstand 75% sulfuric acid for up to thirty days or any organic solvent with a membrane voltage of 1000 psi (6 , 9 MPa) up to 4000 psi (27.6 MPa).

In some non-limiting embodiments of the invention, the polyurethanes and poly (urethane ureas) of the present invention during polymerization can produce a polymerizate having a refractive index of at least 1.55, or at least 1.56, or at least 1.57 , or at least 1.58, or at least 1.59, or at least 1.60, or at least 1.62, or at least 1.65 . In other non-limiting embodiments of the poly (urethane urea) of the present invention, a polymerizate having an Abbe number of at least 32, or at least 35, or at least 38, or at least 39, or at least 40, or at least 44. The refractive index and Abbe number can be determined using methods known in the art, such as the American Standard Test Method ASTM -D 542-00. In addition, the refractive index and the Abbe number can be determined using various known instruments. In a non-limiting embodiment of the present invention, the refractive index and Abbe number can be measured in accordance with ASTM-D 542-00 with the following exceptions: (i) testing one or two samples / examples instead of at least three examples defined in section 7.3; and (ii) the test samples were not conditioned instead of conditioning the samples / examples before testing, as defined in section 8.1. In addition, in a non-limiting embodiment of the invention, an Atago multi-wavelength digital refractometer, model DR-M2, can be used to measure the refractive index and Abbe number of samples / examples.

Solid products that can be prepared using the polyurethanes or poly (urethane ureas) of the present invention include, but are not limited to, optical products or lenses, photochromic products or lenses, windows, portholes such as conventional clear windows, windshields, sidelights and rear lights, aircraft windows, ballistic resistant products, parts of air engines such as vanes, and glazings.

In some non-limiting embodiments, the implementation of the polymeric base material, including the coating composition applied thereto, may be in the form of optical elements such as windows, flat and vision-correcting eye lenses, external surfaces of liquid crystal displays, cathode ray tubes, etc., monitors for TVs and computers, transparent polymer films, transparent products, such as windshields, airplane windows, plastic coatings, etc.

The polyurethanes and poly (urethane ureas) of the present invention are necessary for a wide range of applications. They are especially useful as glazing materials for aircraft windows with safety glass. In addition to glazing aircraft, the polyurethanes and poly (urethane ureas) of the present invention in sheet form can be used in architecture and can be tinted or made opaque by pigmentation, if desired. In such applications, the polyurethanes and poly (urethane ureas) of the present invention can be in sheet form and can be used alone or can be laminated with another material, as discussed above. The layers in the composite may have the same or different elastic modulus values, if desired. In addition, in some embodiments, the polyurethanes and poly (urethane ureas) of the present invention can be used for optical lenses, as they can be optically transparent, not exposed to ultraviolet light and moisture, and resistant to abrasion.

In other non-limiting embodiments, the polyurethanes and poly (urethane ureas) of the present invention can be used as low thermal expansion substrates for applying conductive films for electrochromic applications, microwave absorbing films, and low resistance films. In other non-limiting embodiments, the elongated acrylic base may be coated with the cyanoethyl acrylate / acrylic copolymer and further coated with the polyurethanes and poly (urethane ureas) of the present invention.

The polyurethanes and poly (urethane ureas) of the present invention can be used in sheet form and can vary in thickness from about 2 to about 500 mils, although thinner and thicker sheets can sometimes be used depending on the application. When used for aircraft in some embodiments, the thickness may vary between 1/8 inch and 1/2 inch (from 0.32 to 1.27 cm).

In some embodiments, car windows can be made from a thermoplastic polycarbonate resin, for example, a resin sold under the trade name LEXAN, with the coating composition of the present invention applied as a weatherproof layer to the outside of the window to increase the weather resistance of the window . On the other hand, a car window can be obtained in the form of a glass / LEXAN laminate with glass as the outer layer and a coating composition of the present invention, applied as a layer on the inner side of the laminate.

The coating composition of the present invention can be applied to the surface of the substrate using any known coating technique. It is desirable to spray the coating composition onto the surface of the substrate using an automated spraying system in which the surface tension of the fluid stretches the coherent liquid web over the surface of the substrate while the mechanical spraying device crosses the sheet of substrate. An automatic spraying device usually consists of a hinge bracket that holds the nozzle connected to the pressurized vessel where the resin solution is located. The bracket makes passes along the guide device above the sheet to be coated. The fluid flow rate is controlled using a pressurized vessel. The speed of movement of the hinge bracket is set using a potentiometer. The nozzle distance from the sheet is optimized and kept constant with the help of a hinged bracket. This is especially important for curved sheets. The coating thickness is determined by the initial viscosity of the resin solution and the rate of evaporation of the solvent. The evaporation rate is mainly controlled by the choice of solvent and air flow in cubic feet / min in a ventilated booth for coating. On the other hand, coating compositions can be prepared and poured into the appropriate form to obtain the desired structure, which can then be applied as a layer onto a suitable base, for example, through a lamination process or can be used as a monolithic structure.

The coating composition, as a rule, can itself be applied to the base in the form of a transparent or pigmented monolayer or in the form of a pigmented base layer and / or a transparent top layer in a painted-plus-transparent composite coating, which is known to a person skilled in the art. In some embodiments, the coating may be applied before the isocyanate and hydroxyl groups have fully reacted, for example, by spraying the isocyanate and hydroxyl components individually through a mixing nozzle to coat the substrate. Alternatively, the coating may be partially cured in an oven and then exposed to a high moisture environment, such as a high humidity environment or an aqueous dust medium, for further interaction and curing of the coating. If desired, the coating composition may include additional materials well known in the art of surface coatings, such as surfactants, flow control agents, thixotropic agents, fillers, anti-gas agents, organic co-solvents, catalysts and other common excipients. Such materials may comprise up to 40% by weight of the total weight of the coating composition.

As mentioned above, although the cured compositions can be obtained from liquid coating compositions, they can also be obtained from coating compositions prepared in the form of powder coating compositions.

In another non-limiting embodiment, the cured compositions of the present invention can also be used as decorative or protective coatings for pigmented plastic (elastomeric) substrates or "mold-in-color" (MIC) plastic substrates. In such applications, the compositions may be applied directly to a plastic base or may be incorporated into a forming matrix. Optionally, an adhesion promoter may first be applied directly to the plastic or elastomeric base, and the composition may be applied over it in the form of an upper layer.

In another non-limiting embodiment, the compositions of the present invention can also be used in the form of an anti-cracking layer, an anti-tensile coating layer or an anti-destruction layer for glass or other substrates.

In a non-limiting embodiment, the polyurethane polymerizate of the present invention can be used to produce photochromic products. In another embodiment of the invention, the polymerizate may be transparent to that part of the electromagnetic spectrum that activates the photochromic substance (s), that is, that wavelength of ultraviolet (UV) radiation that gives a colored or open form of the photochromic substance, and that part of the visible spectrum , which includes the wavelength of maximum absorption of the photochromic substance in its UV-activated form, that is, an open form.

Photochromic compounds exhibit a reversible color change when exposed to light that includes ultraviolet rays, such as ultraviolet radiation from sunlight or radiation from a mercury lamp. Various classes of photochromic compounds have been synthesized and proposed for applications in which such a sunlight-induced reversible color change or dimming is desired. The most widely described classes of photochromic compounds are oxazines, pyranes and fulgides.

The general mechanism responsible for the reversible color change, that is, the change in the absorption spectrum in the visible region of the light (400-700 nm), manifested by various types of photochromic compounds, is described and grouped according to common features (see John C. Crano, “Chromogenic Material (Photochromic) ”, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1993, pp. 321-332). The general mechanism for most of the known classes of photochromic compounds, for example indolinospiro pyranes and indolinospirooxazines, includes an electrocyclic mechanism. When exposed to activating radiation, these compounds pass from a colorless compound with a closed cycle to colored samples with an open cycle. On the other hand, the colored form of fulgide photochromic compounds is generated by an electrocyclic mechanism involving the transformation of a colorless open-cycle form into a closed-loop colored form.

A wide range of photochromic compounds can be used in the present invention. In a non-limiting embodiment, organic photochromic compounds or substances may be used. In alternative non-limiting embodiments, photochromic compounds, for example, dissolved, dispersed, or diffused into the polymerizate or coated thereon, may be incorporated.

In a non-limiting embodiment, the organic photochromic substance may have an activated absorption maximum within the visible region of more than 590 nm. In another non-limiting embodiment, the activated absorption maximum within the visible region can be in the range of at least 590 to 700 nm. Such materials may produce cyan, bluish green, or bluish purple when exposed to ultraviolet light in an appropriate solvent or matrix. Non-limiting examples of such substances that can be used in the present invention are, but are not limited to, spiro (indoline) naphthoxazines and spiro (indoline) benzoxazines. These and other suitable photochromic substances are described in US patents: 3562172, 3578602, 4215010, 4342668, 5405958, 4637698, 4931219, 4816584, 4880667, 4818096.

In another non-limiting embodiment, organic photochromic substances can have at least one absorption maximum within the visible region in the range from 400 to less than 500 nm. In another non-limiting embodiment, the substance may have two absorption maxima within this visible range. Such materials may give a yellow-orange color when exposed to ultraviolet light in an appropriate solvent or matrix. Non-limiting examples of such materials may be certain chromenes, such as, but not limited to, benzopyranes and naphthopyranes. Many such chromenes are described in US patents: 3567605, 4826977, 5066818, 4826977, 5066818, 5466398, 5384077, 5238931 and 5274132.

In another non-limiting embodiment, the photochromic substance can have a maximum absorption in the visible region in the range from 400 to 500 nm and a maximum absorption within the visible region in the range from 500 to 700 nm. Such materials give a color (a) ranging from yellow / brown to purple / gray when exposed to ultraviolet light in an appropriate solvent or matrix. Non-limiting examples of such substances may be certain benzopyran compounds having substituents at the 2-position of the pyran ring and a substituted or unsubstituted heterocyclic ring, for example a benzothien or benzofuran ring fused to the benzene portion of benzopyran. Other non-limiting examples of such compounds are disclosed in US patent No. 5429774.

In some non-limiting embodiments, the implementation of the photochromic substance for use in the present invention may be photochromic organometallic dithizonates, such as, but not limited to, aryl hydrazidates (arylazo) thioformic acid, such as, but not limited to, mercury dithizonates, which are described, for example, US Pat. No. 3,361,706. Fulgides and fulgimides, such as, but not limited to, 3-furyl and 3-thienyl fulgides and fulgimides, which are described in US Pat. No. 4,931,220 (column 20, line 5 - column 21, line 38) my ut it is used in the present invention. Relevant parts of the above patents are incorporated by reference.

In other non-limiting embodiments, the implementation of the photochromic products of the present invention may include one photochromic substance or a mixture of several photochromic compounds. In other non-limiting embodiments, the implementation of various mixtures of photochromic substances can be used to obtain activated colors, such as almost neutral gray or brown.

The amount of photochromic substance used may vary. In some non-limiting embodiments, the amount of photochromic substance and the ratio of the substances (for example, when a mixture is used) can be such that the polymerizate on which the substance is applied or in which the substance is incorporated, when activated in direct sunlight, gives the desired color, for example a substantially neutral color, such as shades of gray or brown, that is, as close as possible to the neutral color of these colors of activated photochromic substances. In some non-limiting embodiments, the amount of photochromic substance used may depend on the color intensity of the activated samples and the desired primary color.

In some non-limiting embodiments, the implementation of the photochromic substance can be applied to the polymerizate or included in the polymerizate by various methods that are known in the art. In a non-limiting embodiment, the photochromic substance may be dissolved or dispersed within the polymerizate. In other non-limiting embodiments, the implementation of the photochromic substance can be absorbed into the polymerizate using methods known in the art. The definition of “absorb” or “absorb” includes the penetration of a photochromic substance into the polymerizate without assistance, transfer by absorption with the aid of a solvent of the photochromic substance into the porous polymer, vapor phase transfer and other such transfer mechanisms. In a non-limiting embodiment, the absorption method may include coating a photochromic article from a photochromic substance; heating the surface of the photochromic product and removing the remaining coating from the surface of the photochromic product. In alternative non-limiting embodiments, the absorption process may include immersing the polymerizate in a hot solution of a photochromic substance or thermal transfer.

In some non-limiting embodiments, the implementation of the photochromic substance may be a separate layer between adjacent layers of the polymerizate, for example, as part of a polymer film; or a photochromic substance can be applied as a coating or as part of a coating placed on the surface of the polymerizate.

The amount of photochromic substance or composition containing the photochromic substance deposited or incorporated into the polymerizate may vary. In some non-limiting embodiments of the invention, the amount may be such that upon activation there is a photochromic effect visible to the naked eye. Such an amount can usually be described as a photochromic amount. In some non-limiting embodiments, the amount used may depend on the color intensity desired upon irradiation, and on the method of incorporation or deposition of the photochromic substance. In the general case, the more photochromic material is applied or implanted, the higher the color intensity. In some non-limiting embodiments, the amount of photochromic substance incorporated into or applied to the photochromic optical polymerizate can be from 0.15 to 0.35 mg per square centimeter of the surface onto which the photochromic substance is embedded or applied.

In another non-limiting embodiment, a photochromic substance may be added to the polyurethane prior to polymerization and / or curing of the material by pouring. In such an embodiment, the photochromic substance used can be selected so that it is resistant to potentially harmful interactions, for example, with the isocyanate present. Such harmful interactions can lead to the deactivation of a photochromic substance, for example, by trapping it in either open or closed form.

Other non-limiting examples of suitable photochromic substances for use in the present invention may include photochromic pigments and organic photochromic substances encapsulated in metal oxides, such as those described in US Patent Nos. 4,166,043 and 4,367,170; organic photochromic substances encapsulated in an organic polymerizate, such as those described in US Pat. No. 4,931,220.

The invention is further described below with reference to the examples below. Unless otherwise specified, all parts and percentages are by weight.

EXAMPLES

The physical properties presented below are measured as follows.

Light transmission (%) is measured in accordance with ASTM E903-82.

The yellowness index is measured in accordance with ASTM-D 1925-70.

The refractive index is measured on a Abbe multiwave refractometer, model DR-M2, manufactured by ATAGO Co., Ltd .; the refractive index of liquids is measured in accordance with ASTM-D 1218 and the refractive index of solids is measured in accordance with ASTM-D 542.

The density (g / cm ³ ) of solids is measured in accordance with ASTM-D 792-00.

Taber abrasion (% turbidity) is measured for up to 100 cycles using a Taber abrasive machine that has a 500 g CS-10F abrasive wheel for a 3 × 3 × 1/8 inch sample (7.62 × 7.62 × 0 , 32 cm) in accordance with ASTM-D 1044-99.

Bauer abrasion (% turbidity) is measured in accordance with ASTM F 735-94 (reapproved in 2001).

The crack propagation coefficient K is measured in accordance with U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993).

The tensile strength at yield, the percentage elongation at yield and Young's modulus are measured at approximately 25 ° C in accordance with ASTM-D 638-03.

Gardner impact resistance is measured in accordance with ASTM-D 5420-04.

Dynatup multiaxial toughness is measured in accordance with ASTM-D 3763-02.

Shore hardness is measured in accordance with the guidelines for the Shore D hardness tester.

QUV-B tests are carried out for 1000 hours in accordance with ASTM-G 53.

The glass transition temperature (T _g ) is measured using a dynamomechanical analysis.

The linear coefficient of thermal expansion is measured using a DuPont Thermomechanical Analyzer (TMA) in accordance with ASTM E 228-95.

The following abbreviations are used:

CHDM: 1,4-cyclohexanedimethanol;

Des N 3400: 60% hexamethylene diisocyanate dimer and 40% hexamethylene diisocyanate trimer, commercially available from Bayer;

Des W: 4,4'-methylene bis (cyclohexyl isocyanate) commercially available from Bayer;

MDI: methylenediphenyl-4,4'-diisocyanate;

Polycaprolactone diol: polycaprolactone diol Tone 0210 having a molecular weight of 1000 g / mol, commercially available from Solvay;

Polycarbonate diol 1: polycarbonate diol KM-10-1733 derived from hexanediol having a molecular weight of 1000 g / mol, commercially available from Stahl;

Polycarbonate diol 2: polycarbonate diol KM-10-1667 obtained from hexanediol having a molecular weight of 1000 g / mol, commercially available from Stahl;

TMDI: trimethylhexamethylene diisocyanate;

TMP: trimethylolpropane;

TMXDI: meta-tetramethylsilylene diisocyanate.

Example A

Polyurethanes and poly (urethaneureas) formulations 1-133 are obtained from the components in the amounts listed in tables 1-18.

Polyurethanes (water-free formulations) are prepared in a glass reactor under nitrogen with stirring. The polyisocyanate is preheated before adding other components to a temperature of approximately 100 ° C. The mixture is heated to a temperature of approximately 110 ° C for approximately 10 minutes and maintained at this temperature for approximately 30 minutes.

Poly (urethaneureas) (formulations containing water) are also obtained in a glass reactor under a nitrogen atmosphere with stirring. The polyisocyanate is preheated to a temperature of approximately 60 ° C.

In the case of formulations 123-127, 131, 132 and 133, water is added to the polyisocyanate, the temperature is maintained for approximately 30 minutes, and an urea prepolymer with isocyanate functionality is obtained. Other components are added, the mixture is heated to a temperature of approximately 90 ° C for approximately 10 minutes and maintained at this temperature for approximately 30 minutes.

In the case of formulations 128-130, approximately 0.15 equivalents of trimethylolpropane are added to the polyisocyanate and the temperature is maintained for approximately 120 minutes to form an urethane urea prepolymer with isocyanate functionality. Other components are added, the mixture is heated to a temperature of approximately 110 ° C for 120 minutes and maintained at this temperature for approximately 4 hours.

Each mixture of polyurethane and poly (urethane urea) is degassed to remove carbon dioxide and poured into a casting cell measuring 12 × 13 × 0.125 '' (30.5 × 33 × 0.3 cm), which is preheated to a temperature of approximately 121 ° C. The filled cell is then cured in an oven for approximately 48 hours at approximately 121 ° C.

table 2 Recipe, No. Polyisocyanate Branched polyol Diol Urethane content (wt.%) The content of cyclic groups
(wt.%) Like crosslinking weight (g / mol) The content of hard segments (wt.%) Type of Equ. Type of Equ. Type of Equ. 21 Des w 1.00 TMP 0.3 1,4-butanediol 0.6 27.54 37.81 2142 49.00 Polycarbonate diol 1 0.1 22 Des w 1.00 TMP 0.3 Isopropylidene-dicyclohexanol 0.7 25.79 35.41 2287 77.00 23 Des w 1.00 TMP 0.4 1,10-Decanediol 0.5 25.08 34.44 2352 46.00 Polycarbonate diol 1 0.1 24 Des w 1.00 TMP 0.3 1,10-Decanediol 0.6 24.64 33.83 2395 46.00 Polycarbonate diol 1 0.1 25 Des w 1.00 TMP 0.3 1,4-butanediol 0.5 23.38 32,10 2523 54.00 Polycarbonate diol 1 0.2 26 Des w 1.00 TMP 0.4 1,10-Decanediol 0.6 29.30 40,23 2013 65.00 27 Des w 0.5 TMP 0.3 1,10-Decanediol 0.7 29.13 39,99 2025 MDI 0.5 28 Des w 1.00 TMP 0.3 1,12-Cyclododecandiol 0.7 27.48 37.72 2147 29th TMDI 1.00 TMP 0.2 Chdm 0.8 34.35 47.16 1718 73.00 thirty 1.00 TMP 0.3 Decandiol 0.45 29.34 40.28 2011 Xylene glycol 0.25 31 Des w 0.3 TMP 0.3 1,10-Decanediol 0.7 31,50 43.24 1873 TMDI 0.7 32 Des w 0.8 TMP 0.3 1,10-Decanediol 0.5 27.62 37.92 2136 75.00 Bis (2-hydroxyethyl) terephthalate 0.2 34 Des w 0.75 TMP 0.3 1,10-Decanediol 0.7 28.91 39.69 2041 MDI 0.25

Table 4 Recipe, No. Polyisocyanate Branched polyol Diol Urethane content (wt.%) The content of cyclic groups
(wt.%) Like crosslinking weight (g / mol) The content of hard segments (wt.%) Type of Equ. Type of Equ Type of Equ. 48 Des w 1.00 TMP 0.3 1,4-butanediol 0.35 33.04 45.35 1786 70.00 1,5-pentanediol 0.35 49 Des w 1.00 TMP 0.3 1,5-pentanediol 0.6 32.22 44,23 1831 71.00 1,8-octanediol 0.10 fifty Des w 1.00 TMP 0.3 1,5-pentanediol 0.6 31.97 43.89 1845 71.00 1,10-Decanediol 0.10 51 Des w 1.00 TMP 0.3 1,4-butanediol 0.2 32.84 45.09 1796 71.00 1,5-pentanediol 0.50 52 Des w 1.00 TMP 0.3 1,4-butanediol 0.5 33.23 45.62 1775 70.00 1,5-pentanediol 0.20 53 Des w 1.00 TMP 0.3 1,4-butanediol 0.6 32,99 45.29 1789 70.00 TSGDI 0.10 54 Des w 1.00 TMP 0.3 1,5-pentanediol 0.6 32,23 44.25 1830 71.00 TSGDI 0.10 55 Des w 1.00 TMP 0.3 1,5-pentanediol 0.50 31.88 43.77 1850 71.00 TSGDI 0.20 56 Des w 1.00 TMP 0.3 1,5-pentanediol 0.5 30.09 41.32 1960 71.00 Bis (2-hydroxyethyl) terephthalate 0.20 57 Des w 1.00 TMP 0.3 1,5-pentanediol 0.6 31.19 42.82 1892 73.00 Isopropylidene-dicyclohexanol 0.10 58 Des w 1.00 TMP 0.3 1,5-pentanediol 0.5 22,99 31.56 2566 35.00 Polycarbonate diol 1 0.2 59 Des w 1.00 TMP 0.3 1,5-pentanediol 0.6 29.96 37.01 2188 50.00 Polycarbonate diol 1 0.1 60 Des w 1.00 TMP 0.3 1,5-pentanediol 0.3 26.25 36.04 2247 64.00 TSGDI 0.3 Polycarbonate diol 1 0.10 61 Des w 1.00 TMP 0.4 1,5-pentanediol 0.1 22.55 30.95 2617 37.00 TSGDI 0.3 Polycarbonate diol 1 0.20

Table 8 Recipe, No. Light transmission (%) Yellowing rate Refractive index Density (g / cm ³ ) one 91.84 0.44 1,524 1,1417 2 91.91 0.34 1,531 1,1307 3 91.9 0.33 1,531 1,1388 four 91.88 0.4 1,531 1,1209 5 91.58 0.66 1,544 1,1346 6 91.84 0.37 1,533 1,1261 7 91.87 0.34 1,531 1,1144 8 91.8 1.65 1,524 1,1051 9 91.93 0.5 1,527 1,0912 10 91.72 1.7 1,527 1,0929 fifteen 1,524 1,0969 16 1,52 1,0685 17 1,525 1,1002 eighteen 1,517 1,0976 19 1,521 1,0886 twenty 1,517 1,0979 21 1,517 1,1327 23 1,523 1,1043 24 1,517 1.0971 25 1,521 1,1372 26 1,525 1,0876 29th 1,512 1,0984 thirty 1,531 1,1049 31 1,508 1,072 32 1,527 1,1123 37 1,522 1,086 38 1,522 1,0831 39 1,524 1,0921 40 1,525 1,0846 41 1,522 1,0866 42 1,524 1,0928 43 1,525 1,076 44 1,526 1,0796 58 1,145

Table 13 Recipe, No. Impact Dynatup Shore Hardness Glass transition temperature Coefficient of thermal expansion (inch / inch) one 17.6 79 126 2 24.28 88 119 81.91 3 4.04 88 140 four 25,4 86 117.1 5 8.6 88 156 6 15,2 86 132 7 27,2 86 129.9 8 31.5 82 106 9 38,4 80 99.1 94.65 10 35.5 81 102 fifteen 24.8 80 105 16 34,4 79 93 17 13.9 88 123.9 eighteen 40.9 83 119 19 44.3 81 89.1 twenty 26.1 83 75.1 70.01 21 39.6 81 97 23 17.9 79 87 101.11 24 33,4 80 79.2 97.2 25 44.9 78 76.1 95.66 26 28.6 84 106 29th 5.34 85 71.1 72.36 thirty 30.7 85 120.1 31 41 79 52.1 96.91 32 46.5 82 104 38 33,2 81 111.1 39 32.9 81 103.9 40 41.9 81 101.1 41 27.5 80 42 25.1 81 43 35.3 80 97 44 3.15 86 48 25,2 49 4.24 fifty 26.3 51 21.6 52 31.6 53 22.2 54 26.7 55 41.6 56 20.7

Table 14 Recipe, No. Impact Dynatup Shore Hardness Glass transition temperature Coefficient of thermal expansion (inch / inch) 57 17,2 58 62.3 66 59 36.6 60 37,4 61 38.9 62 152 63 134 64 150 65 174 66 166 67 161 89 42.6 90 48,4 91 50,2 92 48 93 56.5 94 45.1

Table 16 Recipe, No. Light transmission (%) Yellowing rate Refractive index Density (g / cm ³ ) 125 1,119 126 1,125 127 1,133 128 1,113 129 1,128 130 1,113 131 1,127 132 1,129

Table 17 Recipe, No. Taber abrasion Bayer abrasion, turbidity (%) K coefficient Tensile modulus at yield (psi) Elongation at yield (%) Gardner Impact Resistance (inch · lb) Number of cycles Turbidity (%) 125 355,000 13 51 126 1113 305,000 four 24 127 1551 282000 12 244 128 853 369000 16 56 129 686 441000 7.5 8 130 766 389000 fifteen 37 131 290000 7.7 126 132 289000 19 328 133 289000 eleven 224

Table 18 Recipe, No. Impact strength, Dynatup Shore Hardness Glass transition temperature Coefficient of thermal expansion (inch / inch) 125 137 126 14.6 115 127 thirty 67 128 3.31 161 129 3 130 8.67 153 131 32,5 132 133 9.29

The above samples exhibit low yellowing, high light transmission, high impact resistance and good ballistic stability.

Laminate 6`` × 6 '' (15.2 × 15.2 cm) from the 2 '' layer (5.1 cm) of the molded formulation 2 described below, with the outer surface facing outwardly applied to 1 '' (2.5 cm) the molded formulation layer 9 described below and the 0.5 '' (1.3 cm) molded formulation layer 60 stops or deflects four consecutive AK-47 shots (7.62 x 39 mm cartridge) from 150 feet (45.7 m). Each layer is molded as described above. A layer of glass in the laminate is not used. The laminate is heated in an autoclave at approximately 300 ° F (149 ° C) for approximately 2 hours.

Polycast 84 aerospace elongated acrylic polymer samples (commercially available from Spartech of Clayton, Missouri) and Example A polymer samples, Formulation 2 (synthesized at 110 ° C. and cured at 143 ° C. as described above), are evaluated for their physical properties , which are presented below in table 19. The sample of example A, formulation 2, has a lower density, higher impact resistance and elongation and is more stringent than the tested sample of elongated acrylic polymer. LEXAN Polycarbonate # 8574K26 (commercially available from McMaster Carr Supply Co., Cleveland, Ohio) and Example A polymer samples, Formulation 84 (synthesized at 110 ° C. and cured at 143 ° C. as described above), are evaluated for their physical properties, which are presented below in table 20. Example A, formulation 84, has better resistance to solvents, resistance to UV radiation and higher impact resistance than the tested LEXAN sample.

Table 19 Properties Elongated acrylic polymer Formulation Example 2 Example A Light transmission 92 92 Turbidity,% <1% <0.1% Density 1.18 1.13 Resistance to solvent / 75% aqueous sulfuric acid Load 1000-4000 psi K coefficient 2400 1500 Gardner Impact Test (inch · lb) 16 628 High Speed Multiaxial Impact Strength 3.6 (untreated) 26.5 Elongation at break (%) <5 38% Elongation (1000 hours QUV-B) (%) <5 40% Tensile strength 11250 11800 Tensile modulus 450,000 367000 Glass transition temperature 205 247 ° F (119 ° C) Deformation temperature due to thermal heating Puckering up to 180 ° F 235 ° F (113 ° C) Abrasion resistance: turbidity (%), 100 cycles on Taber's abrasive machine thirty fifteen Refractive index 1.49 1,519 Shore Hardness (Shore Hardness D) 94 90

Table 20 Properties Polycarbonate Sample formulation 84, example A Light transmission 88 92 Density 1,2 1,08 Solvent resistant Low with respect to OH, H ⁺ , acetone Satisfactory with respect to OH, H ⁺ , acetone Gardner impact resistance, average fracture energy 588 in. Lbs > 640 in. Lb (> 72 J) High Speed Multiaxial Impact Strength 72 J 105 j Turbidity (%), 100 cycles on Taber's abrasive machine 60% fifteen% Refractive index 1,586 1,519 Tensile modulus 320,000 300,000 Tensile strength 8000 psi 8500 psi Elongation at break (%) one hundred% 200% Elongation (1000 hours QUV-B) (%) Strong destruction, brittleness-yellowness 97% Deformation temperature due to thermal heating 275 ° F 220 ° F Glass transition temperature 305 ° F 240 ° F Shore Hardness (Shore Hardness D) 85 80

DMA Tests

Sample formulation 114 (prepared from 0.95 equivalents of 1,10-decanediol, 0.05 equivalents of trimethylolpropane and 1.0 equivalents of 4,4'-methylene bis (cyclohexyl isocyanate) (DESMODUR W) was evaluated using a dynamic mechanical analysis (DMA) for determination of dynamic elastic modulus, loss modulus and tangential delta (tan delta). DMA is carried out on a solid, fixed sample with dimensions of 2 × 2 × 1/8 '' (5.1 × 5.1 × 0.3 cm), which varies with a frequency of 1 Hz over a wide range of temperatures increased at a rate of 3 ° C / min As shown in FIG.16, the sample exhibits low the phase transition temperature at a loss modulus of about -70 ° C, which is unusual for glassy polymers and indicates molecular mobility during torsion at such a low temperature.The second transition is present at approximately 14 ° C. The glass transition temperature of such a polymer is 71 ° C, which is expressed by the maximum in the tan delta graph.At this temperature, the polymer most effectively translates mechanical vibrations into heat, that is, at this temperature, the polymer reaches its maximum ation. The dynamic modulus of elasticity is the energy stored by the polymer and can be related to the Young's modulus or the stiffness of the polymer.

Ballistic tests

Example AA

The thick sample of Formulation 2 of Example A above, measuring 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm), is cured by heating at 290 ° F (143 ° C) for 48 hours. Four bullets 0 , 40 gauges, fired from a distance of 30 feet (9.1 m) at a speed of 987 ft / s (300 m / s), ricochet from the surface of the sample, and the plastic does not crack. A perspective photograph of the test sample is shown in FIG.

Example AB

A thick sample of formulation 2 of Example A above, measuring 6 × 6 × 3/8 '' (15.2 × 15.2 × 1 cm), was cured by heating at 290 ° F (143 ° C) for 48 hours. Bullet fired from a 12-gauge shotgun from a distance of 20 feet (6.1 m) at a speed of 1290 ft / s (393 m / s) using heavy sports lead pellets, ricochets off the surface of the sample and the plastic does not crack. A perspective photograph of the test sample is shown in FIG. 18.

AC example

A thick sample of formulation 93 of Example A above, measuring 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm), is cured by heating at 290 ° F (143 ° C) for 48 hours. Three caliber bullets 9 mm released from a distance of 20 feet (6.1 m) at a speed of 1350 ft / s (411 m / s) are stuck in the sample. A photograph of a front view of the test sample is shown in FIG. 19.

Example AD

A thick sample of formulation 94 of Example A above, measuring 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm), was cured by heating at 290 ° F (143 ° C) for 48 hours. Caliber 9 bullet mm, released from a distance of 20 feet (6.1 m) at an initial speed of 1350 ft / s (411 m / s), is stuck in the sample. Photographs of the test sample are shown in FIGS. 20 and 21. FIG. 20 is a perspective view of a sample showing a bullet stuck in the surface of the sample. FIGURE 21 is a side view of a sample showing the entry of a bullet into the sample.

Example AE

A thick sample of Formulation 2 of Example A above of dimensions 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) was cured by heating at 290 ° F (143 ° C) for 48 hours. A thick sample of formulation 9 of the above Example A with dimensions of 6 × 6 × 1 '' is cured by heating at 290 ° F (143 ° C) for 48 hours. A thick sample of the formulation 58 of the above Example A with dimensions of 6 × 6 × 0.5 '' (15 , 2 × 15.2 × 1.75 cm) are cured by heating at 290 ° F (143 ° C) for 48 hours. The composite is prepared by assembling a 1 '' (2.5 cm) thick layer of sample 2, 1 ' '(2.5 cm) thick layer sample formulation 9 and 0.5 ”(1.25 s ) Thick layer of the formulation of the sample 58 so that the layer formulation 2 was converted to the rifle.

Four 7.62 × 39 mm cartridges having a steel core are discharged from an AK-47 rifle from a distance of 30 yards (27.4 m) at an initial speed of 2700 ft / s (823 m / s). The first bullet is delayed in the middle of the formulation layer 9, usually parallel to the initial direction of the shot. Bullets from the second to the fourth stop far from layer 58, usually parallel to the initial direction of the shot. Photographs of the test sample are shown in FIGS. 22 and 23. FIG. 22 is a front view of a portion of the sample showing the bullet entry points and two bullets stuck in the surface of the sample. FIG. 23 is a rear view of a sample showing two exiting bullets stuck in a sample formulation layer 58.

AF example

Samples obtained from formulations 58 and 89-97 of Example A above behave similarly, that is, everyone "catches" the bullets. A sample prepared from formulation 94 shows the smallest amount of penetration into the sample, with approximately 1/8 '' of the rear wall of the bullet protruding from the surface. No viscoplastic thickening is observed in the back surface of the sample obtained from formulation 94. Penetration is significantly reduced compared to samples prepared from formulations 58 and 89-92.

Example B

Comparative non-limiting example of a processing temperature of 80 ° C. compared to a temperature of 110 ° C.

Short chain diols (aliphatic diols having 4 to 8 carbon atoms, discussed above), as a rule, do not mix with isocyanates due to the different polarity and the difference in surface tension between the two materials. It has been found that when a short-chain diol and isocyanate are mixed at 80 ° C or less, it takes longer for a clear solution to form than at 110 ° C or higher. Although both solutions may appear transparent, it has been found that there is inhomogeneity, which itself manifests itself in cured products in the form of much lower impact resistance than when preparing solutions at 110 ° C or higher. In addition, when pouring or reactive injection molding into a glass mold, any cooling that occurs as a result of pouring and exposure to air, or a mold temperature below 100 ° C, exacerbates the problem of inhomogeneity, since additional cooling increases this inhomogeneity. If the temperature drops even lower, the short-chain diol and isocyanate will separate into phases and look cloudy. Such turbidity will not be eliminated in a furnace heated to 120-140 ° C after being poured into a mold and heated for 2 to 48 hours. Higher shock resistance fluctuations are also found when process temperatures drop below 100 ° C. In the case of temperatures above 110 ° C, the initial Gardner impact resistance values for the polymers of the present invention are higher initially, and they show less fluctuations in impact resistance from load to load when they are processed at temperatures above 110 ° C. The following examples illustrate the temperature effect considered.

Example B1

The following components: 20.1 g of 1,5-pentanediol, 7.5 g of trimethylolpropane and 72.45 g of DESMODUR W containing 20% of the trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate) are charged into a glass reactor, equipped with a thermocouple and an external mixer. The load was brought to a temperature of 110 ° C to 120 ° C with stirring and connecting a vacuum (2 mm Hg, 266 Pa) to remove bubbles. After reaching a temperature of 110-120 ° C. The load is stirred for 10-20 minutes.

The load is poured into a heated glass mold, which is preheated in an oven at 140 ° C. The polymer was cured for 48 hours at 140 ° C. without catalyst. After curing, the mold is removed from the oven and allowed to cool to room temperature. Then a plastic sheet is removed from the glass mold and cut into 2 × 2 × 1/8 '' (5.1 × 5.1 × 0.3 cm) samples to test the Gardner impact resistance. Gardner's initial impact resistance averages 260 in · lb (30 J).

Example B2

The following components: 20.1 g of 1,5-pentanediol, 7.5 g of trimethylolpropane and 72.45 g of DESMODUR W containing 20% of the trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate) are charged into a glass reactor, equipped with a thermocouple and an external mixer. The load is brought to a temperature of 80 to 90 ° C with stirring and connecting a vacuum (2 mmHg, 266 Pa) to remove bubbles. After reaching a temperature of 80-90 ° C, the load is stirred for 1-2 hours until the load becomes transparent.

The load is poured into a heated glass mold, which is preheated in an oven at 140 ° C. The polymer was cured for 48 hours at 140 ° C. without catalyst. After curing, the mold is removed from the oven and allowed to cool to room temperature. Then, a plastic sheet is removed from the glass mold and cut into 2 × 2 × 1/8 '' (5.1 × 5.1 × 0.3 cm) samples to test the Gardner impact resistance. Gardner's initial impact resistance is on average 62 inches · lb (7 J).

Example B3

The following components: 17.9 g of 1,4-butanediol, 7.4 g of trimethylolpropane and 74.47 g of DESMODUR W containing 20% of the trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate) are loaded into a glass reactor, equipped with a thermocouple and an external mixer. The load was brought to a temperature of 110 ° C to 120 ° C with stirring and connecting a vacuum (2 mm Hg, 266 Pa) to remove bubbles. After reaching a temperature of 110-120 ° C. The load is stirred for 10-20 minutes.

The load is poured into a heated glass mold, which is preheated in an oven at 140 ° C. The polymer was cured for 48 hours at 140 ° C. without catalyst. After curing, the mold is removed from the oven and allowed to cool to room temperature. Then a plastic sheet is removed from the glass mold and cut into 2 × 2 × 1/8 '' (5.1 × 5.1 × 0.3 cm) samples to test the Gardner impact resistance. Gardner's initial impact resistance averages 180 in · lb (21 J).

Example B4

The following components: 17.9 g of 1,4-butanediol, 7.4 g of trimethylolpropane and 74.47 g of DESMODUR W containing 20% of the trans-trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate) are loaded into a glass reactor, equipped with a thermocouple and an external mixer. The load was brought to a temperature of 80 ° C to 90 ° C with stirring and connecting a vacuum (2 mmHg, 266 Pa) to remove bubbles. After reaching a temperature of 80-90 ° C, the load is stirred for 1-2 hours until the load becomes transparent.

The load is poured into a heated glass mold, which is preheated in an oven at 140 ° C. The polymer was cured for 48 hours at 140 ° C. without catalyst. After curing, the mold is removed from the oven and allowed to cool to room temperature. Then, a plastic sheet is removed from the glass mold and cut into 2 × 2 × 1/8 '' (5.1 × 5.1 × 0.3 cm) samples to test the Gardner impact resistance. Gardner's initial impact resistance is on average 10-15 inch · lb (1-1.5 J).

Example C

To estimate the total percentage of the crystalline domains arranged in a row in the polyurethane samples according to the present invention, formulation 2 samples (0.7 equivalents of 1,5-pentanediol (PDO, PDO), 0.3 equivalents of trimethylolpropane (TMP) and 1 equivalent 4.4 'methylene bis (cyclohexyl isocyanate) (DESMODUR W)) and formulations 136 (0.95 equivalents of PDO, 0.05 equivalents of TMP and 1 equivalent of 4.4'-methylene bis (cyclohexyl isocyanate) (DESMODUR W)) were tested using differential scanning calorimetry (DSC) at a speed of 2 ° C / min and using thermogravimetric go analysis (TGA).

Each sample was prepared as follows: all components in the appropriate formulation were mixed at approximately 110 ° C for approximately 30 minutes, degassed in vacuo for approximately 5 to approximately 10 minutes; then poured into a glass mold heated to approximately 200 ° F (93 ° C) and cured for approximately 48 hours, cooled to room temperature (25 ° C) and removed from the mold. Sample formulation 2 is maintained at approximately 25 ° C for approximately seven months.

Sample 136 (aged at approximately 25 ° C. for approximately two weeks) was used as a control sample and its percentage of spaced crystalline domains was used as a reference point for 100% crystallinity. Relatively 100% crystallinity of the sample formulation 136, the proportion of crystalline domains located in a row in the formulation 2, as calculated, is 42%. In the case of both samples, an endothermic peak near ~ 260 ° C was detected, and this peak is attributed to the melting of their ordered domains. DSC data for each of the sample formulations 2 and 136 are presented below in table 21 and FIG 24 and 25, respectively. Thermogravimetric analysis (TGA) for sample formulation 136 is presented in FIG.

Table 21 Generalized DSC Results Sample No. 136 2 Equivalents and
recipe components 0.95 PDO + 0.05 TMP + 1 Des W 0.7 PDO + 0.3 TMP + 1 Des W T _article (° C) 99 Endotherm Peak (° C) 260 260 Heat Capacity (J / g) 3.77 1,63 Calculated crystalline domains (%) 100 (Control) 42

Example D: Ballistic Testing

Example D1

The polyurethane polymer in accordance with the present invention is obtained from the components listed in table 22 below.

Table 22 Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,10-decanediol TMP Des w 205.30 300.00 IT# - - - Acid# - - - Equivalent mass 87 44.00 131.2 Assigned Equivalents 0.7 0.3 1,0 Monomer mass 60.90 13,20 131.20 Bulk% Monomer 29.66% 6.43% 63.91% The mass of monomers during the experiment 88,99 19.29 191.72 Mass% of hard segments 74.40 Bulk% Urethane 28.74 The molecular weight of the crosslinking (g / mol) (M _from ) 2053.00

1,10-Decanediol, trimethylolpropane and DESMODUR W are preheated to 80 ° C and added to a glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30.5 × 30.5 × 0.3 cm), preheated to 121 ° C. The filled cell was cured for 48 hours at 143 ° C.

This recipe with a thickness of 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) withstands a 0.40 caliber pistol shot from a distance of 30 feet (9.1 m) and at a speed of 987 ft / sec without cracking. At a distance of 20 feet (6.1 m), the bullet also stops and no cracking is observed. Multiple shots of 9 mm, 1350 ft / s (411 m / s) from 20 feet (6.1 m) are sustained without cracking. The recipe also withstands 3 consecutive shots of a 12-gauge shotgun (1290 ft / s) from a distance of 30 feet (9.1 m) at 3/8 '' thickness (18 × 12 × 3 / 8``) (46 × 30 × 1 cm) when using a heavy sports lead bullet. In each trial, the bullets ricochet off the target.

Example D2

The polyurethane polymer in accordance with the present invention is obtained from the components listed in table 23 below.

Table 23 Solids The mass of the polymer (g) Set loading size (g) Monomer name PC-1733 1,5-pentanediol TMP Des w 239.04 300.00 IT# - - - - Acid# - - - - Equivalent mass 440 52.08 44.00 131.2 Assigned Equivalents 0.15 0.55 0.3 1,0 Monomer mass 66.00 28.64 13,20 131.20 Bulk% Monomer 27.61% 11.98% 5.52% 54.89% The mass of monomers during the experiment 82.83 35.95 16.57 164.66 Mass% of hard segments 35.84 Bulk% Urethane 24.68 The molecular weight of the crosslinking (g / mol) (M _from ) 2390.4

1,5-Pentanediol, RS-1733, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30.5 × 30.5 × 0.3 cm), preheated to 121 ° C. The filled cell was cured for 48 hours at 143 ° C.

This formulation can withstand multiple shots of a 9 mm bullet (115 grains), 1350 ft / sec, by “capturing” into the polymer volume in samples 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm). Penetration of the bullet is approximately 0.25 '' (0.6 cm) in the absence of viscoelastic swelling in the back of the sample. The same formulation with dimensions of 4 × 4 × 1 '' (10.1 × 10.1 × 2.5 cm) also can withstand multiple shots of 0.40 caliber, in which the bullet is neither captured nor ricocheted. The bullet settles slightly deformed at the base of the sample. With a 3/8 '' (1 cm) thickness, this recipe can withstand 3 shots of a 12-gauge shotgun from a distance of 30 feet (9.1 cm). Most bullets penetrate the surface of the sample.

Example D3

The polyurethane polymer in accordance with the present invention is obtained from the components listed in table 24 below.

Table 24 Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol TMP Des w 175.94 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 44.00 131.2 Assigned Equivalents 0.7 0.3 1,0 Monomer mass 31.54 13,20 131.20 Bulk% Monomer 17.93% 7.50% 74.57% The mass of monomers during the experiment 53.78 22.51 223.71 Mass% of hard segments 70.13 Bulk% Urethane 33.53 The molecular weight of the crosslinking (g / mol) (M _from ) 1759.42

1,4-Butanediol, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell (12 × 12 × 0.125``) (30.5 × 30.5 × 0.3 cm), preheated to 121 ° C. The filled cell was cured for 48 hours at 143 ° C.

This formulation in a 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) sample withstands multiple 0.40 caliber shots from a distance of 30 feet (9.1 m) without cracking. The speed at 0.40 caliber is 987 ft / s (300 m / s). With a thickness of 3/8 '' (1 cm) at a distance of 60 feet (18.2 m), the recipe withstands multiple hits from a 12-gauge shotgun with large bullets at an initial bullet speed of 1290 ft / s (393 m / s). From a distance of 20 feet (6.1 m) and 30 feet (9.1 m), this recipe with a thickness of 1 '' (2.5 cm) is destroyed by 9 mm (115 grains) with a pistol bullet at a speed of 1350 ft / s (411 m) / sec).

Example D4

The polyurethane polymer in accordance with the present invention is obtained from the components listed in table 25 below.

Table 25 Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,5-pentanediol TMP Des w 180.85 300.00 IT# - - - Acid# - - - Equivalent mass 52,075 44.00 131.2 Assigned Equivalents 0.7 0.3 1,0 Monomer mass 36.45 13,20 131.20 Bulk% Monomer 20.16% 7.30% 72.55% The mass of monomers during the experiment 60.47 21.90 217.64 Mass% of hard segments 70.94 Bulk% Urethane 32.62 The molecular weight of the crosslinking (g / mol) (M _from ) 1808.53

1,5-Pentanediol, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell (12 × 12 × 0.125``) (30.5 × 30.5 × 0.3 cm), preheated to 121 ° C. The filled cell was cured for 48 hours at 143 ° C.

This formulation in a 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) sample withstands a 0.40 caliber pistol shot from a distance of 30 feet (9.1 m) and at a speed of 987 ft / s (300 m / s) without cracking. At a distance of 20 feet (6.1 m), the bullet also stops, but there are some small cracks. Multiple shots of 9 mm, 1350 ft / s (411 m / s), from a distance of 20 feet (6.1 m) are maintained without cracking. The recipe also withstands 3 consecutive shots of a 12-gauge shotgun (1290 ft / s, 393 m / s) from a distance of 30 feet (9.1 m) with a thickness of 3/8 '' (1 cm) and when using a heavy sports lead bullet.

Example D5

The polyurethane polymer in accordance with the present invention is obtained from the components listed in table 26 below.

Table 26 Solids The mass of the polymer (g) Set loading size (g) Monomer name KM10-1733 1,5-pentanediol TMP Des w 258.44 300.00 IT# - - - - Acid# - - - - Equivalent mass 440 52,075 44.00 131.2 Assigned Equivalents 0.2 0.5 0.3 1,0 Monomer mass 88.00 26.04 13,20 131.20 Bulk% Monomer 34.05% 10.07% 5.11% 50.77% The mass of monomers during the experiment 102.15 30.22 15.32 152.30 Mass% of hard segments 44,20 Bulk% Urethane 22.83 The molecular weight of the crosslinking (g / mol) (M _from ) 2584.38

1,5-Penanediol, polycarbonate diol KM10-1733, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to a glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell 12 × 12 × 0.125 '' (30.5 × 30.5 × 0.3 cm), pre-heated to 143 ° C. The filled cell was cured for 48 hours at 121 ° C.

This formulation withstands multiple shots of 9 mm (115 grains), 1359 ft / s (393 m / s) by “capturing” into the polymer volume in samples 6 × 6 × 1 '' (15.2 × 15.2 × 2, 5 cm). Bullet penetration is approximately 0.5 '' (1.2 cm) with slight viscoelastic swelling in the back of the sample. The same sample with dimensions of 4 × 4 × 1 '' (10.1 × 10.1 × 2.5 cm) also withstands multiple shots of 0.40 caliber, in which the bullet is neither captured nor ricocheted. The bullet settles slightly deformed at the base of the sample. With a thickness of 3/8 '' (1 cm), this formulation can withstand 3 shots of a 12-gauge shotgun from a distance of 30 feet (9.1 m). Most bullets penetrate the surface of the sample.

All 9 mm shots were fired by bullets weighing 115 grains, an initial speed of 1350 ft / s (411 m / s), which were fired from a 9 mm Ruger pistol. All 0.40-caliber shots were fired from a 0.40-caliber Smith and Wesson pistol with an initial speed of 987 ft / s (300 m / s). All 12-caliber rifle shots were fired from a 12-gauge Remington shotgun using lead bullets, large sporting bullets, with an initial bullet speed of 1290 ft / sec (393 m / sec). Samples were fired that were attached to a 12 '' thick wood block using Velcro ^® without a frame to hold the sample. Shooting is done outdoors at temperatures ranging from about 60 ° F (15 ° C) to about 80 ° F (27 ° C).

Example E

Samples were prepared from formulation 2 of Example A above and tested to determine Gardner impact resistance, as in Example A. Sample E1 was prepared using 35 wt.% Trans, trans-isomer of 4,4'-methylene bis (cyclohexyl isocyanate). Sample E2 was obtained using 17 wt.% Trans, trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate). The Gardner impact resistance of sample E1 is 150 inch · lb (17 J). The Gardner impact resistance of sample E2 is 40 inch · lb (5 J). Sample E1 obtained using a higher weight percent trans, trans-isomer of 4,4'-methylene bis (cyclohexyl isocyanate) has a higher Gardner impact resistance than sample E2, which is obtained with a lower weight percent trans, trans-isomer 4,4'-methylene bis (cyclohexyl isocyanate).

Example F

Samples were obtained from Formulation 1 of Example 1 above with the additional inclusion of 3 wt.% CIBA TINUVIN B75 liquid light stabilizer system (commercially available from Ciba Specialty Chemicals) (which is a mixture of 20 wt.% IRGANOX 1135, 40 wt.% TINUVIN 571 and 40 wt.% TINUVIN 765). Gardner's initial impact resistance is 75 in · lb (9 J). After 1000 hours of QUV-B, the Gardner impact resistance is 75 in · lb (9 J). The initial tensile strength is 13400 psi (92.4 MPa) and after 1000 hours of testing, the QUV-B is 13100 psi (90.3 MPa). The initial elongation is 40% and after 1000 hours of QUV-B test is 50%.

Example G

Examples of Elastoplastic Polyurethane

Example G1

The following reagents: 131.2 g DESMODUR W, 13.41 g trimethylopropane, 26.015 g 1,5-pentanediol and 81.712 g Stahl KM-1733, polycarbonate diol with a molecular weight of 1000 based on hexanediol, mixed together, heated to 80 ° C and degassed . 10 ppm dibutyltin diacetate was added and stirred until the solution became homogeneous. The mixture was poured into a glass mold and cured for 48 hours at 290 ° C (143 ° C). After curing, the mold is allowed to cool to room temperature (25 ° C) and the polymer is removed from the mold. The polymer has a Young's modulus of 215,000 psi (approximately 1482 MPa). The urethane content is 23.4 wt.%. The molecular weight of the crosslinking is 2548 g / mol. The content of cyclic groups is 32 wt.%.

A 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) product made from this polymer stops a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411 m / sec) from a distance of 20 feet (6.1 m), due to the capture of a bullet in the polymer. The back of the bullet penetrates approximately 1/8 '' (0.3 cm) into the specimen with a very slight rise on the back wall.

Example G2

The following reagents: 131.2 g DESMODUR W, 13.41 g trimethylopropane, 28.096 g 1,5-pentanediol and 65.370 g Stahl KM-1733, polycarbonate diol with a molecular weight of 1000 based on hexanediol, mixed together, heated to 80 ° C and degassed . 10 ppm dibutyltin diacetate was added and stirred until the solution became homogeneous. The mixture was poured into a glass mold and cured for 48 hours at 290 ° C (143 ° C). After curing, the mold is allowed to cool to room temperature (25 ° C) and the polymer is removed from the mold. The polymer has a Young's modulus of 215,000 psi (approximately 1482 MPa). The urethane content is 24.8 wt.%. The molecular weight of the crosslinking is 2404 g / mol. The content of cyclic groups is 34 wt.%.

A 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) product made from this polymer stops a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411 m / sec) from a distance of 20 feet (6.1 m), due to the capture of a bullet in the polymer. Four fifths (4/5) of the length of the bullet penetrates the sample, with the back of the bullet protruding approximately (0.3 cm) from the exposed surface.

Example G3

The following reagents: 131.2 g DESMODUR W, 13.41 g trimethylopropane, 28.617 g 1,5-pentanediol and 61.284 g Stahl KM-1733, polycarbonate diol with a molecular weight of 1000 based on hexanediol, mixed together, heated to 80 ° C and degassed . 10 ppm dibutyltin diacetate was added and stirred until the solution became homogeneous. The mixture was poured into a glass mold and cured for 48 hours at 290 ° C (143 ° C). After curing, the mold is allowed to cool to room temperature (25 ° C) and the polymer is removed from the mold. The polymer has a Young's modulus of 215,000 psi (approximately 1482 MPa). The urethane content is 25.15 wt.%. The molecular weight of the crosslinking is 2369 g / mol. The content of cyclic groups is 34.53 wt.%.

A 6 × 6 × 1 '' (15.2 × 15.2 × 2.5 cm) product made from this polymer stops a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411 m / sec) from a distance of 20 feet (6.1 m), due to the capture of a bullet in the polymer. Four fifths (4/5) of the length of the bullet penetrates the sample, with the back of the bullet protruding approximately 1/8 '' (0.3 cm) from the impacted surface.

Examples of poly (urethane urea)

Example G4

The following reagents: 318.26 g of DESMODUR W and 0.84 g of trimethylopropane containing 0.5% dibutyltin diacetate were charged into a glass reactor, heated and stirred at 75 ° C. Deionized water (4.37 g) is added, mixed and the reaction is carried out to obtain hard polyurea segments in a polyurethane prepolymer. The carbon dioxide foam is removed in vacuo. Then increase the temperature to 80 ° C and carry out the reaction for 30 minutes. The gases were removed using a vacuum of 2 mmHg and 63.42 g of 1,5-pentanediol were added together with 32.76 g of trimethylolpropane. The mixture is stirred and the vacuum is slowly increased. The exothermic temperature reaches 95 ° C, and at this time the mixture is poured into a glass mold measuring 6 × 6 × 1/8 '' (15.2 × 15.2 × 0.3 cm). The material was cured at 290 ° F (143 ° C) for 48 hours. The material is removed from the mold at room temperature (25 ° C), and a transparent, light-transmitting plastic is obtained.

Example G5

The following reagents: 2.23 g of trimethylolpropane are reacted with 76.133 g of DESMODUR W containing 10 ppm dibutyltin diacetate at 80 ° C to form a branched polyurethane ending in isocyanate groups. Water (0.9 g) was added to the charge after lowering the temperature to 60 ° C and the reaction was carried out for 2 hours to obtain the polyurea portion of the polyurethane-polyurea prepolymer. Then carbon dioxide is removed in vacuo, 38 g of trimethylolpropane are added, stirred, degassed in vacuo and poured into the glass form described above at 75 ° C. After curing for 48 hours at 290 ° F (143 ° C), the plastic is removed from the mold at room temperature (25 ° C) to obtain a light-transmitting plastic with a high modulus of elasticity. Young's modulus is 441,000 psi when measured on an Instron tensile testing machine at a traverse speed of 6 '' / min.

Example G6

The following reagents: 2.23 g of trimethylolpropane, are reacted with 131.2 g of DESMODUR W using 10 parts by weight of dibutyltin diacetate based on the total charge to give a branched, isocyanate-terminated polyurethane prepolymer. Deionized water (1.34 g) was added and the reaction was carried out at 60 ° C. Carbon dioxide is removed by degassing in a vacuum. The temperature was raised to 75 ° C and 39.66 g of cyclohexanedimethanol was added as a chain extender. After stirring and degassing, the liquid was poured into the glass form described above and cured at 290 ° F (143 ° C) for 48 hours. Extraction from the mold is carried out at room temperature (25 ° C) to obtain a plastic sheet with high optical characteristics.

Example H

Example H1

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol TMP Des w 175.94 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 31.54 13,20 131.20 Bulk% Monomer 17.93% 7.50% 74.57% The mass of monomers during the experiment 53.78 22.51 223.71

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C and for 6 hours at 150 ° C. Gardner average impact resistance is 102 in · lb (12 J).

Example H2

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol TMP Des w 175.94 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 31.54 13,20 131.20 Bulk% Monomer 17.93% 7.50% 74.57% The mass of monomers during the experiment 53.78 22.51 223.71 Mass% of hard segments 70.13 Bulk% Urethane 33.53 (M _from ) 1759.42

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner's average impact resistance is 110 in · lb (13 J).

Example H3

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol TMP Des w 175.94 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 31.54 13,20 131.20 Bulk% Monomer 17.93% 7.50% 74.57% The mass of monomers during the experiment 53.78 22.51 223.71 Mass% of hard segments 70.13 Bulk% Urethane 33.53 (M _from ) 1759.42

1,4-Butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 131 in · lb (15 J).

Example H4

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,5-pentanediol TMP Des w 180.85 300.00 IT# - - - Acid# - - - Equivalent mass 52,075 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 36.45 13,20 131.20 Bulk% Monomer 20.16% 7.30% 72.55% The mass of monomers during the experiment 60.47 21.90 217.64 Mass% of hard segments 70.94 Bulk% Urethane 32.62 (M _from ) 1808.53

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 135 in · lb (15 J).

Example H5

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,5-pentanediol TMP Des w 178.43 300.00 IT# - - - Acid# - - - Equivalent mass 52,075 44.00 131.2 Assigned Equivalents 0.4000 0,600 1,000 Monomer mass 20.83 26.40 131.20 Bulk% Monomer 11.67% 14.80% 73.53% The mass of monomers during the experiment 35.02 44.39 220.59 Mass% of hard segments 41.09 Bulk% Urethane 33.07 (M _from ) 892.15

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 71 in · lb (8 J).

Example H6

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Chdm 1,5-pentanediol TMP Des w 187.86 300.00 IT# - - - - Acid# - - - - Equivalent mass 72.11 52,075 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 25.24 18.23 13,20 131.20 Bulk% Monomer 13.43% 9.70% 7.03% 69.84% The mass of monomers during the experiment 40.30 29.11 21.08 209.51 Mass% of hard segments 37.88 Bulk% Urethane 31.41 (M _from ) 1878.65

1,5-Pentanediol, CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 143 in · lb (16 J).

Example H7

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Chdm TMP Des w 194.88 352.00 IT# - - - Acid# - - - Equivalent mass 72.11 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 50,48 13,20 131.20 Bulk% Monomer 25.90% 6.77% 67.32% The mass of monomers during the experiment 91.17 23.84 236.98 Mass% of hard segments 73.03 Bulk% Urethane 30.28 (M _from ) 1948.77

CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 63 in · lb (7 J).

Example H8

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Monomer name Chdm 1,4-butanediol TMP Des w 185.41 IT# - - - - Acid# - - - - Equivalent mass 72.11 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 25.24 15.77 13,20 131.20 Bulk% Monomer 13.61% 8.51% 7.12% 70.76% The mass of monomers during the experiment 40.84 25.52 21.36 212.29 Mass% of hard segments 38.38 Bulk% Urethane 31.82 (M _from ) 1854.10

1,4-Butanediol, CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 47 in · lb (5 J).

Example H9

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,6-hexanediol TMP Des w 185.76 300.00 IT# - - - Acid# - - - Equivalent mass 59.09 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 41.36 13,20 131.20 Bulk% Monomer 22.27% 7.11% 70.63% The mass of monomers during the experiment 66.80 21.32 211.88 Mass% of hard segments 71.71 Bulk% Urethane 31.76 (M _from ) 1857.63

1,6-Hexanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 130 in · lb (15 J).

Example H10

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,6-hexanediol 1,4-butanediol TMP Des w 180.85 300.00 IT# - - - - Acid# - - - - Equivalent mass 59.09 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 20.68 15.77 13,20 131.20 Bulk% Monomer 11.44% 8.72% 7.30% 72.55% The mass of monomers during the experiment 34.31 26.16 21.90 217.64 Mass% of hard segments 91.09 Bulk% Urethane 32.62 (M _from ) 1808.53

1,6-Hexanediol, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 53 in · lb (6 J).

Example H11

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Chdm 1,6-hexanediol TMP Des w 190.32 300.00 IT# - - - - Acid# - - - - Equivalent mass 72.11 59.09 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 25.24 20.68 13,20 131.20 Bulk% Monomer 13.26% 10.87% 6.94% 68.94% The mass of monomers during the experiment 39.78 32.60 20.81 206.81 Mass% of hard segments 96.51 Bulk% Urethane 31.00 (M _from ) 1903.20

1,6-Hexanediol, CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 124 in · lb (14 J).

Example H12

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-cyclohexanediol TMP Des w 185.06 352.00 IT# - - - Acid# - - - Equivalent mass 58.08 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 40.66 13,20 131.20 Bulk% Monomer 21.97% 7.13% 70.90% The mass of monomers during the experiment 77.33 25.11 249.56 Mass% of hard segments 71.60 Bulk% Urethane 31.88 (M _from ) 1850.56

1,4-Cyclohexanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 95 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner impact resistance is 7 inch · lb (1 J).

Example H13

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Ethylene glycol TMP Des w 166.12 300.00 IT# - - - Acid# - - - Equivalent mass 31,035 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 21.72 13,20 131.20 Bulk% Monomer 13.08% 7.95% 78.98% The mass of monomers during the experiment 39.23 23.84 236.93 Mass% of hard segments 68.36 Bulk% Urethane 35.52 (M _from ) 1661.25

Ethylene glycol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 4 in · lb (4 J).

Example H14

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol Pentaerythritol Des w 172.95 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 34.04 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 31.54 10.21 131.20 Bulk% Monomer 18.24% 5.90% 75.86% The mass of monomers during the experiment 54.71 17.71 227.58 Mass% of hard segments 71.34 Bulk% Urethane 34.11 (M _from ) 2306.04

1,4-Butanediol, pentaerythritol and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 150 ° C. Pentaerythritol does not dissolve in any way.

Example H15

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-Benzenedimethanol TMP Des w 192.76 300.00 IT# - - - Acid# - - - Equivalent mass 69,085 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 48.36 13,20 131.20 Bulk% Monomer 25.09% 6.85% 68.06% The mass of monomers during the experiment 75.26 20.54 204.19 95.81 Mass% of hard segments 72.73 Bulk% Urethane 30.61 (M _from ) 1927.60

1,4-Benzenedimethanol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 63 in · lb (7 J).

Example H16

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Chdm 1,4-benzene-dimethanol TMP Des w 193.82 300.00 IT# - - - - Acid# - - - - Equivalent mass 72.11 69,085 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 25.24 24.18 13,20 131.20 Bulk% Monomer 13.02% 12.48% 6.81% 67.69% The mass of monomers during the experiment 39.07 37.43 20.43 203.08 Mass% of hard segments 98.38 Bulk% Urethane 30,44 (M _from ) 1938.18

1,4-Benzenedimethanol, CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 75 in · lb (9 J).

Example H17

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-benzene-dimethanol 1,4-butane diol TMP Des w 184.35 300.00 IT# - - - - Acid# - - - - Equivalent mass 69,085 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 24.18 15.77 13,20 131.20 Bulk% Monomer 13.12% 8.55% 7.16% 71.17% The mass of monomers during the experiment 39.35 25.66 21.48 213.51 Mass% of hard segments 93.16 Bulk% Urethane 32.00 (M _from ) 1843.51

1,4-Benzenedimethanol, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 ”(30 × 30 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner Impact Resistance is 62 in · lb (7 J).

Example H18

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Monomer name 1,4-Benzenedimethanol 1,6-hexanediol TMP Des w 189.26 IT# - - - - Acid# - - - - Equivalent mass 69,085 59.09 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 24.18 20.68 13,20 131.20 Bulk% Monomer 12.78% 10.93% 6.97% 69.32% The mass of monomers during the experiment 38.33 32.78 20.92 207.97 Mass% of hard segments 95.93 Bulk% Urethane 31.17 (M _from ) 1892.61

1,4-Benzenedimethanol, 1,6-hexanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner impact resistance is 64 in · lb (7 J).

Example H19

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 4,4'-Trimethylene-dipiperidine TMP Des w 213.80 300.00 IT# - - - Acid# - - - Equivalent mass 99.14 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 69.40 13,20 131.20 Bulk% Monomer 32.46% 6.17% 61.37% The mass of monomers during the experiment 97.38 18.52 184.10 Mass% of hard segments 75,42 Bulk% Urethane 27.60 (M _from ) 2137.98

4,4'-Trimethylene dipiperidine, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. The initial temperature is approximately 50 ° C. With stirring, it rises sharply to 60 ° C, and the reaction medium is gelled into a white mass.

Example H20

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-bis (hydroxyethyl) piperazine TMP Des w 205.38 300.00 IT# - - - Acid# - - - Equivalent mass 87.12 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 60.98 13,20 131.20 Bulk% Monomer 29.69% 6.43% 63.88% The mass of monomers during the experiment 89.08 19.28 191.64 Mass% of hard segments 74.41 Bulk% Urethane 28.73 (M _from ) 2053.84

1,4-bis (Hydroxyethyl) piperazine, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C, while the viscosity rises to the point where the mixture is no longer mixed. The mixture does not become transparent, and the mixture contains unmelted 1,4-bis (hydroxyethyl) piperazine.

Example H21

Polyurethane is prepared from the following components:

Solids Monomer name N, N'-bis (2-Hydroxy-ethyl) oxamide 1,4-butanediol TMP Des w IT# - - - - Acid# - - - - Equivalent mass 88.08 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 30.83 15.77 13,20 131.20 Bulk% Monomer 16.14% 8.26% 6.91% 68.69% The mass of monomers during the experiment 22.60 11.56 9.68 96.17 - 11.61 4.83 47.94 Mass% of hard segments 40.18 Bulk% Urethane 30.89 (M _from ) 1909.99

N, N'-bis (2-Hydroxyethyl) oxamide, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C, while the viscosity rises to the point where the mixture is no longer mixed. The mixture does not become transparent, and unmelted N, N'-bis (2-hydroxyethyl) oxamide is present in the mixture.

Example H22

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 3,6-Dithia-1,2-octanediol TMP Des w 208.52 300.00 IT# - - - Acid# - - - Equivalent mass 91.6 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 64.12 13,20 131.20 Bulk% Monomer 30.75% 6.33% 62.92% The mass of monomers during the experiment 92.25 18,99 188.76 - Mass% of hard segments 74.79 Bulk% Urethane 28.29 (M _from ) 2085,20

3,6-Dithia-1,2-octanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C, while the viscosity rises to the point where the mixture is no longer mixed. The mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 81 in · lb (9 J).

Example H23

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Monomer name 3,6-Dithia-1,2-octanediol bis (4- (2-hydroxy-ethoxy) -3,5-dibromophenyl) sulfone Chdm TMP Des w 258.90 IT# - - - - - Acid# - - - - - Equivalent mass 91.6 326,985 72.11 44.00 131.2 Assigned Equivalents 0.2333 0.2333 0.2333 0,300 1,000 Monomer mass 21.37 76.30 16.83 13,20 131.20 Bulk% Monomer 8.26% 29.47% 6.50% 5.10% 50.68% The mass of monomers during the experiment 24.77 88.41 19.50 15.30 152.03 300.00 Mass% of hard segments 99.10 Bulk% Urethane 22.79 (M _from ) 2588.96

3,6-Dithia-1,2-octanediol, bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) sulfone, CHDM, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to a glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C.

Example H24

Prepare a polyurethane polymer in accordance with the present invention from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 2,2-thiodiethanol TMP Des w 187.17 200.00 IT# - - - Acid# - - - Equivalent mass 61.10 44.00 131.2 Assigned Equivalents 0.7000 0,300 1,000 Monomer mass 42.77 13,20 131.20 Bulk% Monomer 22.85% 7.05% 70.10% The mass of monomers during the experiment 45.70 14.11 140.20 Mass% of hard segments 71.92 Bulk% Urethane 31.52 (M _from ) 1871.67

2,2-Thiodiethanol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 95 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. The Gardner impact value is 5 inch · lb (1 J) and the sample is fragile.

Example H25

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Thiodiethanol 1,4-butanediol TMP Des w 181.56 300.00 IT# - - - - Acid# - - - - Equivalent mass 61.1 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 21.39 15.77 13,20 131.20 Bulk% Monomer 11.78% 8.69% 7.27% 72.26% The mass of monomers during the experiment 35.34 26.06 21.81 216.79 Mass% of hard segments 37.07 Bulk% Urethane 32,50 (M _from ) 1815.56

Thiodiethanol, 1,4-butanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 39 in · lb (4 J).

Example H26

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Thiodiethanol 1,6-hexanediol TMP Des w 186.47 300.00 IT# - - - - Acid# - - - - Equivalent mass 61.1 59.09 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 21.39 20.68 13,20 131.20 Bulk% Monomer 11.47% 11.09% 7.08% 70.36% The mass of monomers during the experiment 34.41 33.27 21.24 211.08 Mass% of hard segments 36.09 Bulk% Urethane 31.64 (M _from ) 1864.67

Thiodiethanol, 1,6-hexanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. The mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '' (30 × 30 × 0.3 cm), previously heated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 55 in · lb (6 J).

Example H27

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,4-butanediol Des N 3400 Des w 182.80 300.00 IT# - - - Acid# - - - Equivalent mass 45.06 153.00 131.2 Assigned Equivalents 1,0000 0,300 0.700 Monomer mass 45.06 45.90 91.84 Bulk% Monomer 24.65% 25.11% 50.24% The mass of monomers during the experiment 73.95 75.33 150.72 Mass% of hard segments 96,42 Bulk% Urethane 32.28 (M _from ) 1828.00

1,4-Butanediol, Des N 3400 and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C. The mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 35 inch · lb (4 J).

Example H28

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name H ₂ O 1,4-butanediol TMP Des w 163.32 300.00 IT# - - - - Acid# - - - - Equivalent mass 9.01 45.06 44.00 131.2 Assigned Equivalents 0.3500 0.3500 0,300 1,000 Monomer mass 3.15 15.77 13,20 131.20 Bulk% Monomer 1.93% 9.66% 8.08% 80.33% The mass of monomers during the experiment 5.79 28.97 24.25 240,99 Mass% of hard segments 79.41 Bulk% Urethane 36.12 (M _from ) 1633.25

1,4-Butanediol, TMP, DESMODUR W (preheated to 80 ° C) and deionized water are added to a glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 105 ° C and allow the components to combine. After combining the components, condensation (water) is observed on the walls of the reactor.

Example H29

Polyurethane is prepared from the following components:

Component Equivalent mass Equivalents Mass (g) Weight (%) TMP 44.7 0.05 2.2 1.3 1,4-butanediol 45 0.95 42.8 24.3 Des w 131 1,0 131 74,4

1,4-Butanediol, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 110 ° C. The mixture is degassed and poured into a casting cell measuring 15 × 15 × 0.125 '' (38 × 38 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 300 in · lb (35 J). W _u is 33.5%, W _s is 46%, and M _s is 10.569 g / mol.

Example H30

Polyurethane is prepared from the following components:

Component Equivalent mass Equivalents Mass (g) Weight (%) TMP 44.7 0.05 2.2 1,2 1,5-pentanediol 52 0.95 49.5 27.1 Des w 131 1,0 131 71.7

1,5-Pentanediol, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 110 ° C. The mixture is degassed and poured into a casting cell measuring 15 × 15 × 0.125 '' (38 × 38 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is 400 in · lb (46 J). W _u is 32.3%, W _s is 44.3%, and M _s is 10.973 g / mol.

Example H31

Polyurethane is prepared from the following components:

Component Equivalent mass Equivalents Mass (g) Weight (%) TMP 44.7 0.05 2.2 1,0 1,10-Decanediol 87 0.95 82.8 38.3 Des w 131 1,0 131 60.6

1,10-Decanediol, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 110 ° C. The mixture is degassed and poured into a casting cell measuring 15 × 15 × 0.125 '' (38 × 38 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. Gardner average impact resistance is> 640 in · lb (> 74 J). W _u is 27.3%, W _s is 37.5%, and M _s is 12.974 g / mol. The impact strength of Dynatup is 77 J.

Example H32

Polyurethane is prepared from the following components:

Component Equivalent mass Equivalents Mass (g) Weight (%) TONE 210 406.4 0.2 81.3 32.3 1,5-pentanediol 52 0.5 26.0 10.3 TMP 44.7 0.3 13,4 5.3 Des w 131 1,0 131 52.0

TONE 210, 1,5-pentanediol, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 110 ° C. The mixture is degassed and poured into a casting cell measuring 15 × 15 × 0.125 '' (38 × 38 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. W _u is 23.4%, W _s is 32%, and M _s is 2542 g / mol.

Example H33

Polyurethane is prepared from the following components:

Component Equivalent mass Equivalents Mass (g) Weight (%) TONE 210 406.4 0.15 61.0 26.1 1,5-pentanediol 52 0.55 28.6 12,2 TMP 44.7 0.3 13,4 5.7 Des w 131 1,0 131 56.0

TONE 210, 1,5-pentanediol, TMP and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 110 ° C. The mixture is degassed and poured into a casting cell measuring 15 × 15 × 0.125 '' (38 × 38 × 0.3 cm), preheated to 121 ° C. The casting is cured for 48 hours at 121 ° C. W _u is 25.2%, W _s is 34.6%, and M _s is 2342 g / mol.

Example I

Samples of formulations 1-10 of example A, plexiglass (Plexiglas from McMasterCarr, Poly 84, elongated acrylic polymer) and LEXAN industrial grade tested to determine the coefficient K in accordance with the following conditions:

Torque Sensor: 2000 lbf;

Humidity (%): 50;

Temperature: 73 ° F (23 ° C);

Test Speed: 320 lbf / min;

Thickness: 0.120 ''

Experience, Sample, Width Thickness Crack Load Time K coefficient No. ID (inch) (inch) (inch) (lb) (sec) 34 1A 2,138 0.123 0.575 345,800 345,800 1296,220 36 1B 2,144 0.122 0,600 318,400 318,400 1241,140 35 1C 2,135 0.128 0.700 294,200 294,200 1199,424 31 2A 1,995 0.123 0.750 304,400 304,400 1477,415 33 2B 1,990 0.131 0.650 322,100 322,100 1330,586 32 2C 1,965 0,132 0.750 278,700 278,700 1279,169 29th 3A 1,986 0.125 0.475 216,400 216,400 777,079 thirty 3B 1,972 0.130 0.425 228,200 228,200 746,028 one 3C 1,988 0.127 0.750 175,600 117,067 822,370 26 4A 2,017 0.125 0,600 327,500 327,500 1321,788 27 4B 2,009 0,120 0.750 276,500 276,500 1359,195 28 4C 2,023 0.123 0.675 283,500 283,500 1259,891 24 5A 2,023 0.122 0,600 20,9,4 157,050 866,505 23 5B 2,020 0,120 0.750 179,900 107,940 874,598 25 5C 2,056 0.166 0.700 205,100 205,100 967,357 fourteen 6A 2,053 0.124 0.650 291,000 218,250 1225,187 16 6B 2,039 0.122 0.670 245,900 245,900 1086,512 fifteen 6C 2,068 0.127 0.690 271,100 232,371 1144,531 12 7A 2,024 0.127 0.620 277,600 185,067 1125,576 13 7B 2,034 0.130 0.750 288,300 192,200 1288,378 eleven 7C 2,019 0.128 0.750 278,700 101,345 1276,297 10 8A 2,006 0.124 0.960 238,400 158,933 1388,038 9 8B 2,021 0.124 0,800 284,600 87,569 1402,845 2 8C 2,009 0.118 0.750 355,400 266,550 1776,120 6 9A 2,003 0.118 0.520 1179,000 428,727 4681,823 8 9B 2,020 0.123 0.670 345,800 106,400 1525,675 7 9C 1,992 0.118 0.450 1220,000 395,676 4486,874 3 10A 2,010 0.116 0.750 782,300 586,725 3956,318 four 10B 2,021 0.119 0.450 742,600 270,036 2655,849 5 10C 2,023 0.119 0.450 756,000 274,909 2700,237 21 11A 2,011 0,132 0.650 272,200 98,982 1106,454 22 11B 2,006 0.130 0.650 220,700 115,148 910,576 twenty 11C 2,011 0.130 0.650 255,000 78,462 1048,797 19 12A 2,019 0.134 0.650 873,600 268,800 3470,984 17 12B 2,021 0,132 0.680 798,900 290,509 3313,758 eighteen 12C 2,023 0.133 0.710 863,400 313,964 3655,555 37 13A 2,036 0.125 1,500 1435,000 521,818 15960,663 38 13B 2,024 0,126 1,500 1,401,000 262,688 15670,107 39 13C 2,024 0.133 1,500 1456,000 273,000 15489,381

Example j

Polyurethane is prepared from the following components:

Solids The mass of the polymer (g) Set loading size (g) Monomer name 1,5-pentanediol TMP Des w 2100,00 IT# - - - Acid# - - - Equivalent mass 52,075 44.00 131.2 Assigned Equivalents 0.4000 0,600 1,000 Monomer mass 20.83 26.40 131.20 178.43 (amount) Bulk% Monomer 11.67% 14.80% 73.53% The mass of monomers during the experiment 245.15 310.71 1544.13 Mass% of hard segments 41.09 0.4 (131 + 52) / 178.43 Bulk% Urethane 33.07 59 g / equiv. / 178.43 g / equiv. (M _from ) 892.15 178.43 / 0.2 mol TMP

1,5-Pentanediol, trimethylolpropane and DESMODUR W (preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 115 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 14 × 14 × 0.375 '', previously heated to 121 ° C. The first set of samples was cured for 48 hours at 121 ° C. The second set of samples was cured for 48 hours at 121 ° C and for 12 hours at 145 ° C. Each sample set is evaluated for stress cracking resistance by immersion for 30 minutes in a 75% aqueous solution of sulfuric acid. A second set of samples can withstand 30 minutes at 4000 psi.

Example K

Trimethylolpropane (0.05 equivalents), 1.10-decanediol (0.95 equivalents) and DESMODUR W (1.0 equivalent, preheated to 80 ° C) are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to 110 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '', previously heated to 143 ° C. The filled cell was cured for 48 hours at 121 ° C. Dynatup multiaxial toughness is 77 J when measured in accordance with ASTM-D 3763-02. The multiaxial toughness Dynatup of the LEXAN sample is 72 J.

Example L

An isocyanate-functional urethane prepolymer is prepared in a glass reactor in vacuo using 0.3 equivalents of 1,5-pentanediol, 1.0 equivalents of Desmodur W and 10 ppm dibutyltin diacetate as reagents. The reaction temperature was maintained at 143 ° C. for 10 hours, and 0.4 equivalents of 1,5-pentanediol and 0.3 equivalents of trimethylolpropane were added. After 30 minutes at 110 ° C, the mixture was poured between grease-coated glass molds and cured for 29 hours at 290 ° F (143 ° C). The mold is removed from the oven and the plastic is removed. Gradner impact resistance is 256 in · lb (29 J).

An isocyanate-functional urethane prepolymer is prepared in a glass reactor in vacuo using 0.5 equivalent of 1,5-pentanediol, 1.0 equivalent of Desmodur W and 10 ppm dibutyltin diacetate as reagents. The reaction temperature was maintained at 143 ° C. for 10 hours, and 0.2 equivalents of 1,5-pentanediol and 0.3 equivalents of trimethylolpropane were added. After approximately 30 minutes at 110 ° C, the mixture was poured between grease-coated glass molds and cured for 72 hours at 290 ° F (143 ° C). The mold is removed from the oven and the plastic is removed. Gradner impact resistance is 256 in · lb (29 J).

A sample prepared from an urethane prepolymer with isocyanate functionality, having a higher amount (0.5 equivalent) of 1,5-pentanediol, has a higher Gardner impact strength. Without being tied to any theory, it is believed that the miscibility between the components is improved due to the preliminary interaction of part of the short-chain diol with the polyisocyanate.

Examples M

Example M1

An isocyanate functional prepolymer (NCO / OH ratio of 3.8) having an equivalent weight of 327 g / mol is obtained by the reaction of the following components:

Component %, mass Equivalent mass Equivalents DESMODUR W
(4,4'-methylene bis (cyclohexyl isocyanate) 54.42 131.2 0.42 DBT FASTCAT 4202
(dibutyltin dilaurate) 0.005 PLURACOL E400NF
(polyethylene glycol) 5,095 200 0,03 PLURONIC L62D
(ethylene oxide / propylene oxide block copolymer) 33.97 1180 0,03 TRIMETHYLPROPAN 2,32 45 0.05 SARA 2077A
polycaprolactone polyol 1.23 375 0.003 IRGANOX 1010 0.49 CYASORB UV 5411 0.97 TINUVIN 328 1.46 IRGANOX MD 1024 0.05 TOTAL 100,000000

at a temperature of approximately 104 ° C for approximately 5 hours. All components are mixed together, with the exception of stabilizers, which are dissolved after the prepolymer has reacted.

Approximately 9 g of acrylamide is dissolved in approximately 45 g of 1,4-butanediol at a temperature of approximately 25 ° C. and mixed with approximately 365 g of the prepolymer obtained above and approximately 0.1% by weight of azobisisobutyronitrile (AIBN) based on solids. The mixture is poured into a glass mold and heated in an oven at a temperature of approximately 80 ° C for approximately 48 hours with constant stirring. A clear polymerizate forms. A cured polymer sample is tested to evaluate light transmission and impact resistance according to Gradner. The light transmission of the sample is 91%, and the impact resistance according to Gardner is equal to 150 inch · lb (17 J).

Example M2

The polyurethane polymer in accordance with the present invention is obtained from the above-described prepolymer with isocyanate functionality, cyclohexane dimethanol (CHDM) and 1,4-butanediol, which are presented below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer Chdm 1,4-butanediol 417.53 200.00 IT# - - - Acid# - - - Equivalent mass 365.71 72.11 45.06 Assigned Equivalents 1.00 0.25 0.75 Monomer mass 365.71 18.03 33.80 Bulk% Monomer 87.59% 4.32% 8.09% The mass of monomers during the experiment 175.18 8.64 16.19

The prepolymer, CHDM (preheated to 80 ° C) and 1,4-butanediol are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 40 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.6 cm) and aluminum cups preheated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C.

A 6 × 6 × 1 '' (15 × 15 × 2.5 cm) product made from this polymer stops a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411 m / s) from a distance 20 feet (6.1 m), with minimal surface damage. The same specimen withstands a 0.40-caliber shot with minor surface damage. Bullets do not ricochet and do not penetrate into the polymer. Bullets fall slightly deformed at the bottom of the sample.

Example M3

The polyurethane polymer in accordance with the present invention is obtained from the above-described prepolymer with isocyanate functionality, cyclohexane dimethanol (CHDM) and 1,4-butanediol, which are listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer Chdm 1,4-butanediol 424.30 200.00 IT# - - - Acid# - - - Equivalent mass 365.71 72.11 45.06 Assigned Equivalents 1.00 0.50 0.50 Monomer mass 365.71 36.06 22.53 Bulk% Monomer 86.19% 8.50% 5.31% The mass of monomers during the experiment 172.38 17.00 10.62

The prepolymer, CHDM (preheated to 80 ° C) and 1,4-butanediol are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 40 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.6 cm) and aluminum cups preheated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C.

Example M4

The polyurethane polymer in accordance with the present invention is obtained from the above-described prepolymer with isocyanate functionality and hydroquinone bis (hydroxyethyl) ester, which are listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer bis (hydroxyethyl ether) hydroquinone 483.40 250.00 IT# - - Acid# - - Equivalent mass 384.29 99.11 Assigned Equivalents 1.00 1.00 Monomer mass 384.29 99.11 Bulk% Monomer 79.50% 20.50% The mass of monomers during the experiment 198.74 51.26

The prepolymer and hydroquinone bis (hydroxyethyl) ester are added to a glass reactor and placed in a heating jacket. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 85 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is placed in a vacuum and degassed, then poured into a casting cell measuring 6 × 6 × 0.25 '' (15 × 15 × 0.6 cm), previously heated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C. The cast sample is transparent, but exhibits some turbidity. Gardner Impact Resistance is 320 in · lb (37 J).

Example N

An isocyanate-functional prepolymer is prepared by the reaction of the following components:

Component %, mass Equivalent mass Equivalents DESMODUR W
(4,4'-methylene bis (cyclohexyl isocyanate) 54.42 131.2 0.42 DBT FASTCAT 4202
(dibutyltin dilaurate) 0.005 PLURACOL E400NF
(polyethylene glycol) 5,095 200 0,03 PLURONIC L62D
(ethylene oxide / propylene oxide block copolymer) 33.97 1180 0,03 TRIMETHYLPROPAN 2,32 45 0.05 SARA 2077A
Polycaprolactone polyol 1.23 375 0.003 TOTAL 100,000000

at a temperature of approximately 104 ° C for approximately 5 hours. All components are mixed together, with the exception of stabilizers, which are dissolved after the prepolymer has reacted.

The polyurethane polymer in accordance with the present invention is obtained from the above prepolymer and 1,4-butanediol, which are listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer 1,4-butanediol 375.38 100.00 IT# - - Acid# - - Equivalent mass 330.32 45.06 Assigned Equivalents 1.00 1.00 Monomer mass 330.32 45.06 Bulk% Monomer 88.00% 12.00% The mass of monomers during the experiment 88.00 12.00

The prepolymer and 1,4-butanediol are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 45 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell with dimensions (4 '' × 4 '' × 60 mils), preheated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C.

A 6 × 6 × 1 '' (15 × 15 × 2.5 cm) product made from this polymer stops a 9 mm (125 grains) bullet fired at an initial speed of 1350 ft / s (411 m / s) from a distance 20 feet (6.1 m), with minimal surface damage. The same specimen withstands a 0.40-caliber shot with minor surface damage.

Examples About

Example O1

An isocyanate-functional prepolymer is prepared by the reaction of the following components:

at a temperature of approximately 104 ° C for approximately 5 hours. All components are mixed together, with the exception of stabilizers, which are dissolved after the prepolymer has reacted.

The polyurethane polymer in accordance with the present invention is obtained from the prepolymer and CHDM described above, which are listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer Chdm 402.98 800.00 IT# - - Acid# - - Equivalent mass 330.87 72.11 Assigned Equivalents 1.00 1,0000 Monomer mass 330.87 72.11 Bulk% Monomer 82.11% 9.01% The mass of monomers during the experiment 656.85 143.15

The prepolymer and CHDM are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 55 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 13 × 13 × 0.25``, previously heated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C.

Example O2

The polyurethane polymer in accordance with the present invention is obtained from the prepolymer and CHDM described above, which are listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Prepolymer 2,2-thiodiethanol 391.97 700.00 IT# - - Acid# - - Equivalent mass 330.87 61.10 Assigned Equivalents 1.00 1,0000 Monomer mass 330.87 61.10 Bulk% Monomer 84.41% 15.59% 590.89 109.11 The mass of monomers during the experiment - -

The prepolymer and 2,2-thiodiethanol are added to the glass reactor. In a nitrogen atmosphere and with constant stirring, the mixture is heated to ~ 55 ° C and allow the components to combine. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 13 × 13 × 0.25``, previously heated to 80 ° C. The filled cell was cured for 24 hours at 121 ° C.

Example P

As a comparative example, a thermoplastic polymer is prepared using 1.0 equivalent of 1.10-decanediol and 1.0 equivalent of Desmodur W as reagents and 10 ppm dibutyltin diacetate as a catalyst. The polymer is mixed at 110 ° C. in a glass reactor in vacuo. After approximately 30 minutes at 110 ° C, the mixture was poured between grease-coated glass molds and cured for 72 hours at 290 ° F (143 ° C). The mold is removed from the oven and the plastic is removed. Gradner impact resistance is less than 40 inch · lb (5 J), and the average value is approximately 16 inch · lb (2 J).

The polymer of the present invention is prepared in a similar manner using a small amount of a branched polyol, namely 0.05 equivalent of trimethylolpropane, as well as 0.95 equivalent of 1,10-decanediol and 1.0 equivalent of Desmodur W. The Gardner impact resistance is 640 in · lb in the case of branched thermoplastics with a molecular weight of crosslinking of approximately 12900 g / mol.

Example Q

Comparative example

For comparison, a prepolymer is prepared by reacting approximately 0.1 equivalent of trimethylolpropane with approximately 1.0 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate) (DESMODUR W) to form polyurethane polyisocyanate dissolved in excess (0.9 equiv.) DESMODUR W. Add approximately 10 ppm dibutyltin diacetate as catalyst. With rapid stirring at room temperature, approximately 0.1 equivalent of 4,4'-methylene-bis-cyclohexylamine, a diamine analogue of DESMODUR W, is added. A white, scaly precipitate forms immediately. The precipitate concentration increases when standing overnight, and the precipitate does not dissolve when heated to approximately 290 ° F (143 ° C). The above example is repeated in the same order as described above, but the polyisocyanate is heated to approximately 40 ° C. With rapid stirring, diamine is added and a similar white precipitate forms which cannot be dissolved by heating to approximately 290 ° F (143 ° C).

In accordance with the present invention, the same polyisocyanate as described above is heated to about 40 ° C. About 0.1 equivalents of water are quickly added with stirring. A vacuum (4 mmHg) is connected to remove carbon dioxide, and the polyurea formed in the polyurethane gives a polyurethane polyurea polyisocyanate, which has a slight turbidity. The diamine analogue of DESMODUR W is formed in situ when water reacts. The mixture is then reacted with 0.8 equivalents of trimethylolpropane to form plastic with a high modulus of elasticity and with high optical transparency. The light transmission of the sample with a thickness of 1/8 '' (0.3 cm) is 91.8% with a turbidity of less than 0.1%. The glass transition temperature is 175 ° C.

In accordance with the present invention, the same polyisocyanate is reacted with 0.2 equivalents of water at about 40 ° C. and carbon dioxide is removed in vacuo. The diamine analogue of DESMODUR W is formed in situ when water reacts. Then, approximately 0.5 equivalents of pentanediol and approximately 0.2 equivalents of trimethylolpropane are reacted with polyurethane-polyurea-polyurea-polyisocyanate to obtain a plastic with high optical transparency, with a transmittance of 91.74% in the case of a 1/8 '' (0.3 cm) sample and temperature glass transitions of approximately 137 ° C.

R examples

Example R1

The following are loaded into a glass reactor with a nitrogen atmosphere with stirring: 8.26 wt.% 3,6-dithia-1,2-octanediol (91.6 equiv. Mass); 29.47 wt.% Bis (4- (2-hydroxyethoxy) -3,5-dibromo-phenyl) sulfone (326.985 equiv. Mass); 6.50 wt.% 1,4-cyclohexanedimethanol (CHDM) (72.1 equiv. Mass); 5.10 wt.% Trimethylolpropane (44 equiv. Mass); 50.68 wt.% 4,4'-methylene bis (cyclohexyl isocyanate) (DESMODUR W) (131.2 equiv. Mass), preheated to a temperature of 80 ° C. The mixture is heated to a temperature of 115 ° C.

The mixture is then degassed and poured into a casting cell measuring 12 × 13 × 0.125 '' (30 × 33 × 0.3 cm), preheated to a temperature of 121 ° C. The filled cell is then cured in an oven for 48 hours at 121 ° C.

The refractive index of the obtained lens is measured as n _D = 1.5519.

Example R2

The following are charged into a glass reactor with a nitrogen atmosphere with stirring: 30.75 wt.% 3,6-dithia-1,2-octanediol (91.6 equiv. Mass); 6.23 wt.% TMP (44.0 equiv. Mass) and 62.92 wt.% DESMODUR W (131.2 equiv. Mass), preheated to a temperature of 80 ° C. The mixture is heated to a temperature of 105 ° C.

The mixture is then degassed and poured into a casting cell measuring 12 × 13 × 0.125 '' (30 × 33 × 0.3 cm), preheated to a temperature of 121 ° C. The filled cell is then cured in an oven for 48 hours at 121 ° C.

The refractive index of the obtained lens is measured as n _D = 1.5448, and the impact resistance is 82.0 inch · lb (9 J).

Example R3

The following are charged into a glass reactor with a nitrogen atmosphere with stirring: 9.70 wt.% 1,5-pentanediol (52.1 equiv. Mass); 7.03 wt.% TMP (44.0 equiv. Mass); 13.43 wt.% CHDM (72.1 equiv. Mass) and 69.84 wt.% DESMODUR W (131.2 equiv. Mass), preheated to a temperature of 80 ° C. The mixture is heated to a temperature of 105 ° C.

The mixture is then degassed and poured into a casting cell measuring 12 × 13 × 0.125 '' (30 × 33 × 0.3 cm), preheated to a temperature of 121 ° C. The filled cell is then cured in an oven for 48 hours at 121 ° C.

Impact resistance is 160.0 in · lb (18 J).

Example R4

This example is carried out in accordance with the procedure of example 3 except that instead of 1,5-pentanediol, 1,4-butanediol (45.1 eq. Mass) is used and CHDM is not present in the mixture. 17.18% 1,4-butanediol, 7.23% trimethylolpropane and 75.48% DESMODUR W.

The impact resistance is 120.0 in · lb (14 J).

Example R5

This example is carried out in accordance with the procedure of example 4 except that instead of 1,4-butanediol, 1,4-benzenedimethanol (69.1 equiv. Mass) is used. 25.09 wt.% 1,4-benzenedimethanol, 6.85 wt.% Trimethylopropane and 74.57 wt.% DESMODUR W.

Impact resistance is 72.0 in · lb (8 J). It was found that after fifteen minutes in the curing cycle, the material becomes cloudy. Therefore, during the rest of the curing cycle, the temperature in the furnace is increased to 143 ° C, but the material remains cloudy.

Example R6

This example is carried out in accordance with the procedure of example 5 except that 1,4-butanediol (45.1 equiv. Mass) is also added to the mixture and the mixture is heated to a temperature of 115 ° C instead of 105 ° C. 13.12 wt.% 1,4-benzenedimethanol, 8.55 wt.% 1,4-butanediol, 71.17 wt.% DESMODUR W.

Impact resistance is 72.0 in · lb (8 J).

Example R7

This example is carried out in accordance with the procedure of example 6 except that instead of 1,4-butanediol 1,6-hexanediol (59.1 equiv. Mass) is used. 12.76 wt.% 1,4-benzenedimethanol, 10.93 wt.% 1,6-hexanediol and 69.32 wt.% DESMODUR W.

Impact resistance is 64.0 in · lb (7 J).

Example R8

This example is carried out in accordance with the procedure of example 7 except that thiodiethanol (61.1 eq. Mass) is used instead of 1,4-benzenedimethanol and the mixture is heated to a temperature of 105 ° C instead of 115 ° C. 11.78% by weight of 2,2-thiodiethanol, 8.69% by weight of 1,4-butanediol, 7.27% by weight of trimethylolpropane and 70.10% by weight of DESMODUR W.

Impact resistance is 72.0 in · lb (8 J).

Example R9

This example is carried out in accordance with the procedure of example 3 except that CHDM is not present in the mixture and the mixture is heated to a temperature of 115 ° C instead of 105 ° C. 20.16 wt.% 1,5-pentanediol, 7.3 wt.% Trimethylolpropane and 72.55 wt.% DESMODUR W.

Impact resistance is 200.0 in · lb (23 J).

Example R10

This example is carried out in accordance with the procedure of example 9 except that instead of 1,5-pentanediol, 1,8-octanediol (73.1 eq. Mass) is used. 26.14 wt.% 1,8-octanediol, 6.75 wt.% Trimethylolpropane and 67.11 wt.% DESMODUR W.

Impact resistance is 624.0 in · lb (72 J).

Example R11

This example is carried out in accordance with the procedure of example 10 except that instead of 1,8-octanediol, 1,10-decanediol (87.1 equiv. Mass) is used. 29.66% by weight of 1,10-decanediol, 6.43% by weight of trimethylolpropane and 63.9% by weight DESMODUR W.

Impact resistance is 624.0 in · lb (72 J).

Example R12

This example is carried out in accordance with the procedure of example 11 except that ethylene glycol (31.0 eq. Mass) is used instead of 1,10-decanediol and the mixture is heated to a temperature of 105 ° C instead of 115 ° C. 13.06 wt.% Ethylene glycol, 7.95 wt.% Trimethylolpropane and 78.99 wt.% DESMODUR W.

Impact resistance is 8.0 inch · lb (1 J).

Example R13

This example is carried out in accordance with the methodology of example 11 except that 1.12-dodecandiol is used instead of 1,10-decanediol. 32.87 wt.% 1.12-dodecanediol, 6.14 wt.% Trimethylolpropane and 60.99 wt.% DESMODUR W.

Impact resistance is 624.0 in · lb (72 J).

Example R14

This example is carried out in accordance with the procedure of example 13 except that instead of 1,12-dodecanediol, 1,6-hexanediol (59.1 equiv. Mass) is used and the mixture is heated to a temperature of 105 ° C instead of 115 ° C. 22.24 wt.% 1,6-hexanediol, 7.11 wt.% Trimethylolpropane and 70.65 wt.% DESMODUR W.

Impact resistance is 144.0 in · lb (17 J).

Example R15

This example is carried out in accordance with the procedure of example 9. Impact resistance is 80.0 inch · lb (9 J).

Example R16

This example is carried out in accordance with the methodology of example 11 except that 101.2 equiv. mass of 1,10-decanediol and KM-1733 (carbonatiol with MM 1000 made from hexanediol and diethyl carbonate and which is commercially available from ICI) (428 equiv. mass). 28.29% by weight of 1,10-decanediol, 9.48% by weight of PC-1733, 5.69% by weight of trimethylolpropane and 56.54% by weight DESMODUR W.

Impact resistance is 640.0 in · lb (74 J).

Example 17

Formulations 1-11 are prepared in accordance with the procedure of Example 3 except that the components listed in Table 21 are used to obtain the reaction mixture. The obtained properties (tensile strength at yield,% elongation at yield, tensile strength at break ,% elongation at break and Young's modulus measured in accordance with ASTM-D 638-03; Gardner impact resistance measured in accordance with ASTM-D 5420-04; T _g measured using dynamomechanical analysis and density are measured in accordance with ASTM-D 792) for formulations 1-11 are presented in tables 27-29.

Table 27 Recipe, No. Component Equivalent Weight (g / eq.) Equivalents Weight Wt% W _u  (%) W _c  (%) M _c  (g / mol) one TMP 44.7 0.3 13.40 6.5 28.7 39,4 2055 1,10-Dodecandiol 87.1 0.7 60.97 29.7 DESMODUR W 131.0 1,0 131.0 63.8 2 TMP 44.7 0.3 13.40 6.7 29.4 40,4 2006 1,10-Dodecandiol 87.1 0.35 30.48 15,2 1,8-octanediol 73.1 0.35 25.58 12.7 DESMODUR W 131.0 1,0 131.0 65,4 3 TMP 44.7 0.3 13.40 7.61 33.5 46.04 1759 1,4-butanediol 45.0 0.7 31.5 17.9 DESMODUR W 131.0 1,0 131.0 74.49 four TMP 44.7 0.3 13.40 7.40 32.6 44.8 1808 1,5-pentanediol 52.0 0.7 36,4 20,13 DESMODUR W 131.0 1,0 131.0 72.47 5 TMP 44.7 0.6 26.82 11.64 33.0 45.81 1786 1,5-pentanediol 52.0 0.4 20.8 15.06 DESMODUR W 131.0 1,0 131.0 73.3 6 TMP 44.7 0.3 13.40 7.20 31.77 43.62 1857 1,6-hexanediol 59.0 0.7 41.3 22.26 DESMODUR W 131.0 1,0 131.0 70.54 7 TMP 44.7 0.3 13.40 6.81 30,44 1938 1,4-CHDM 72.11 0.35 25.24 13.02 1,6-BDM 69.08 0.35 24.18 12.48 DESMODUR W 131.0 1,0 131.0 131.0

Table 28 Recipe, No. Component Equivalent Weight (g / eq.) Equivalents Weight Wt% W _u  (%) W _c  (%) M _c  (g / mol) 8 TMP 1,4-CHDM 72.11 0.35 25.24 13.43 1,5-pentanediol 52.0 0.35 18.23 9.70 9 TMP 44.7 0.3 13.40 6.94 31,0 42.55 1903 1,4-CHDM 72.11 0.35 25.24 13.26 1,6-hexanediol 59.09 0.35 20.68 10.87 DESMODUR W 131.0 1,0 131.0 68.94 10 TMP 1,8-octanediol DESMODUR W 44.7 0.3 13,20 6.7 30,2 41,4 1956 73.1 0.7 51.17 26.2 eleven TMP 131.0 1,0 1,0 67.1 3,6-Dithia-1,2-octanediol DESMODUR W 44.7 0.3 13.40 6.33 28.29 38.84 2085 91.6 0.7 64.12 30.75 Note: Formulation 11 has a refractive index of 1.55 and Gardner impact resistance of 65 inch · lb.

Example R18

This example is carried out in accordance with the procedure of example 12 except that instead of ethylene glycol, 53.0 equiv. the mass of diethylene glycol and the mixture is heated to a temperature of 115 ° C instead of 105 ° C.

Impact resistance is 6.0 in · lb.

Example R19

This example is carried out in accordance with the procedure of example 18 except that instead of diethylene glycol, 67.0 equiv. dipropylene glycol masses.

Impact resistance is 8.0 inch · lb.

After curing, a set of sheets coated with each of AD polymers is subjected to abrasion tests using the standard Taber abrasion test with CS10F grinding wheels (one pair for all samples), each 500 g circle. The grinding wheel is ground before each cycle ( 25 cycles). The tests are carried out at a temperature in the range of from about 70 ° F to about 75 ° F and at a relative humidity of from about 50% to about 60%. The average haze from the scattered light is determined for a given number of Taber cycles; the results are presented below.

The standard QUV-B exposure test procedure for 1000 hours corresponds to approximately three years of external exposure. The results are presented below.

Exposed samples: 1000 hours of exposure. QUV-B - 3 years of external exposure. Sample Covered Turbidity (%) at the number of cycles 0 one hundred 300 500 1000 Polymer A Polymer B Polymer C Polymer D

Examples S: Fire Test

Example S1

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

Solids The mass of the polymer (g) Set loading size (g) Monomer name Bis (2-hydroxy-ethyl) tetrabromobisphenol A ester 1,6-hexane diol TMP Des w 291.54 100.00 IT# - - - - Acid# - - - - Equivalent mass 315.99 59.09 44.00 131.2 Assigned Equivalents 0.4000 0.5000 0,100 1,000 Monomer mass 126.40 29.55 4.40 131.20 Bulk% Monomer 43.35% 10.13% 1.51% 45.00% The mass of monomers during the experiment 43.35 10.13 1.51 45.00 - Bulk% Urethane 20.24 The molecular weight of the crosslinking (g / mol) (M _from ) 8746,23

1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor together with tetrabromobisphenol A solid bis (2-hydroxyethyl) ether. When stirred on a hot plate, the mixture is heated until it becomes transparent and all solid bis (2-hydroxyethyl) ester of tetrabromobisphenol A will not dissolve / not melt.

Gardner's initial impact resistance data show higher impact resistance than elongated acrylic polymer (> 16 inch · lb) and much higher than PLEXIGLAS (2 inch · lb). Fire tests with a Bunsen burner show that the flame immediately extinguishes itself.

Example S2

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

Solids Set loading size (g) Monomer name Bis (2-hydroxyethyl) ester of tetrabromobisphenol A 1,6-hexanediol TMP Des w 475.00 IT# - - - - Acid# - - - - Equivalent mass 315.99 59.09 44.00 131.2 Assigned Equivalents 0.4500 0.4500 0,100 1,000 Monomer mass 142.20 26.59 4.40 131.20 Bulk% Monomer 46.72% 8.74% 1.45% 43.10% The mass of monomers during the experiment 221.90 41.49 6.87 204.74 - Bulk% Urethane 19.38 The molecular weight of the crosslinking (g / mol) (M _from ) 9131.58

The polymer weight is 304.39 g. 1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor together with tetrabromobisphenol A solid bis (2-hydroxyethyl) ether. Under nitrogen and with constant stirring the mixture is heated to ~ 105 ° C until it becomes transparent and the whole solid tetrabromobisphenol A bis (2-hydroxyethyl) ether dissolves / does not melt. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '', previously heated to 121 ° C. The filled cell was cured for 48 hours at 121 ° C. Initial impact resistance data indicate very poor properties (<16 in · lb). Fire tests with a Bunsen burner show that the flame immediately extinguishes itself.

Example S3

The polyurethane polymer in accordance with the present invention is obtained from the components listed below:

Solids Set loading size (g) Monomer name Bis (2-hydroxyethyl) ester of tetrabromobisphenol A 1,6-hexanediol TMP Des w 300.00 IT# - - - - Acid# - - - - Equivalent mass 315.99 59.09 44.00 131.2 Assigned Equivalents 0.1000 0.8000 0,100 1,000 Monomer mass 31.60 47.27 4.40 131.20 Bulk% Monomer 14.73% 22.04% 2.05% 61.17% The mass of monomers during the experiment 44,20 66.12 6.15 183.52 - Bulk% Urethane 27.51 The molecular weight of the crosslinking (g / mol) (M _from ) 6434.13

The polymer weight is 214.47 g. 1,6-Hexanediol, trimethylolpropane and DESMODUR W, preheated to 80 ° C, are added to the glass reactor together with tetrabromobisphenol A solid bis (2-hydroxyethyl) ether. Under nitrogen and with constant stirring the mixture is heated to ~ 105 ° C until it becomes transparent and the whole solid tetrabromobisphenol A bis (2-hydroxyethyl) ether dissolves / does not melt. After the mixture becomes transparent, the mixture is degassed and poured into a casting cell measuring 12 × 12 × 0.125 '', previously heated to 121 ° C. The filled cell was cured for 48 hours at 121 ° C. Fire tests with a Bunsen burner show that the polymer is carbonized and burns approximately 7 seconds after the flame has been removed.

Example T

Fiberglass Reinforced Polyurethane

The following reagents: 208 g of 1,10-decanediol (2.39 equivalents) and 45.7 g of trimethylolpropane (1.02 equivalents) are charged to a flask and heated to 125 ° C. under nitrogen with stirring. When a clear, homogeneous melt forms, the mixture is cooled to 105 ° C. and 446 g (3.41 equivalents) of DESMODUR W are added. After stirring for 15 minutes and reheating to approximately 90 ° C., the mixture becomes clear. After keeping at 90 ° C for approximately 10 minutes, approximately 50% of the liquid is transferred by vacuum into a mold measuring 20 × 20 × 1/8 '' (50.8 × 50.8 × 0.3 cm) containing 4 layers Bidirectional E-fiber mat coated with removable fabric and flow cells inside the vacuum bag. The mold and glass are preheated to 105 ° C before starting the transfer.

After approximately 15 minutes, a sufficient amount of material is transferred to a fully filled bag and impregnated with fiberglass. The bag and mold are then heated at 143 ° C. for 48 hours. The temperature of the obtained fiberglass-polyurethane composite is then reduced to 120 ° C and held for 1 hour, after which the temperature is further reduced to 38 ° C. After 1 hour at 38 ° C, the system was cooled to room temperature and disassembled. The resulting part is stiff, colorless and solid.

Example U

Laminated composite film cast according to the present invention on an elongated acrylic polymer

The casting cell was collected using 0.5 '' elongated acrylic polymer Polycast 84 ^® and 0.25 '' glass which is coated to release dimethyldichlorosilane. For good adhesion of the polyurethane to the elongated acrylic polymer, a primer is applied. The cell measures 6 × 6 '' with a 0.060 '' gap between the glass and the elongated acrylic polymer, which is held constant with a silicone rubber pad. The edges are clamped. A composition using 0.3 equivalent of trimethylolpropane, 0.7 equivalent of 1,5-pentanediol and 1.0 equivalent of DESMIDUR W is mixed and degassed at 210 ° F and poured into the described casting cell. The composition was cured at 180 ° F for 3 days, allowed to cool to room temperature, and then the molded plastic film was separated from the sheet of release glass. Get a composite with high optical characteristics, which has excellent adhesion to the base and high resistance to crack propagation under stress and when exposed to solvents.

The composite is subjected to a load of 4000 psi with tensile stress polyurethane plastic and ethyl acetate is applied, coated with a glass slide and held for 30 minutes. When examined under a microscope, cracking is not observed. The same test is carried out on an uncovered elongated acrylic polymer, on which the formation of cracks immediately visible without a microscope is immediately observed. The same test is carried out on an uncovered elongated acrylic polymer with a load of 1000 psi. Cracks visible without a microscope also occur immediately.

Examples V

Reinforced Composites

As for table 30, the thermoset polyurethanes are prepared as follows.

The reaction vessel is equipped with a stirrer, thermocouple, nitrogen inlet, receiver and vacuum pump. Then load A is added, stirred with heating to 80-100 ° C in vacuo and incubated for 1 hour. Then the reaction mixture is cooled to 80 ° C, the vacuum is turned off and load B is added to the reaction vessel. Then the reaction mixture is heated to 80 ° C in vacuum and an exothermic reaction is allowed to take place with increasing temperature from 110 ° C to 120 ° C. The reaction mixture is poured into the space between two 5 × 5 × 3/16 inch plates of float glass, which are equipped with seals on three sides and held together by clamps. Both glass plates have a silane lubricant deposited on their surface in contact with polyurethane. The space between the plates is approximately three sixteen inches. The casting cell is preheated before casting to a temperature of approximately 120 ° C. After casting, the assembly is subjected to 24-hour curing at 120 ° C, and then 16-hour curing at 143 ° C. After curing, the cell is subjected to a two-hour cycle of gradual cooling from 143 ° C to 45 ° C, leaving it in the oven. The cell is removed from the oven and the glass plates are separated from the polyurethane.

Table 30 Download A Mass parts 1,10-Decanediol 61.00 Trimethylolpropane 13.41 Download To Desmodur W ¹ 131.00 ¹ bis (4-isocyanatocyclohexyl) methane from Bayer Material Science

Example v

The following examples illustrate the incorporation of various inorganic particulate phases into a thermosetting polymer phase. Thermosetting polymers are contacted with various swelling solvents and various precursors that form an inorganic particulate inorganic phase.

Example V1

The introduction of tetramethylorthosilicate in methanol

The thermosetting polyurethane of Example A was immersed in a solution containing 20.3 wt.% (25 vol.%) Anhydrous methanol and 79.7 wt.% (75 vol.%) Tetramethylorthosilicate (TMOS) for 24 hours. Polyurethane is removed from the methanol / TMOS mixture solution and placed in deionized water for three days. The polyurethane is then placed in a vacuum oven at 100 ° C for 2 hours. Transmission electron microscopy (TEM) data indicates that silica particles are introduced into the polyurethane phase. In a polyurethane base, silicon dioxide particles of 250 microns are formed. The morphology of silicon dioxide nanoparticles is generally spherical, and the particle size is in the range from 10 to 20 nm. In this sample, discrete particles and clusters are observed.

Example V2

The introduction of tetraethylorthosilicate in ethanol

The thermosetting polyurethane of Example A was immersed in a solution containing 21.9 wt.% (25 vol.%) Anhydrous ethanol and 78.1 wt.% (75 vol.%) Tetraethylorthosilicate (TEOS) for 24 hours. Polyurethane is removed from the ethanol / TEOS mixture solution and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. TEM data show that silicon dioxide nanoparticles are introduced into the polyurethane phase. The size of the nanoparticles is in the range of 10 to 70 nm, with most being in the range of 10 nm.

Example V3

The introduction of tetramethylorthosilicate in xylene

The thermosetting polyurethane of Example A was immersed in a solution containing 21.7 wt.% (25 vol.%) Anhydrous xylene and 78.3 wt.% (75 vol.%) Tetramethylorthosilicate (TMOS) for 24 hours. Polyurethane is removed from the xylene / TMOS mixture solution and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. TEM data show that silicon dioxide nanoparticles are introduced into the polyurethane phase. The size of the nanoparticles is in the range from 7 to 40 nm.

Example V4

The introduction of tetramethylorthosilicate in ethyl acetate

The thermosetting polyurethane of Example A was immersed in a solution containing 22.4 wt.% (25 vol.%) Anhydrous ethyl acetate and 77.6 wt.% (75 vol.%) Tetramethylorthosilicate (TMOS) for 24 hours. Polyurethane is removed from the ethyl acetate / TMOS mixture solution and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. TEM data show that silicon dioxide nanoparticles are introduced into the polyurethane phase.

Example V5

The introduction of tetramethylorthosilicate in dimethyl sulfoxide

The polyurethane of example A is immersed in a solution containing 25 wt.% (25 vol.%) Anhydrous dimethyl sulfoxide (DMSO) and 75 wt.% (75 vol.%) Tetramethylorthosilicate (TMOS) for 24 hours. Polyurethane is removed from a solution of a mixture of DMSO / TMOS and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. TEM data show that silicon dioxide nanoparticles are introduced into the polyurethane phase. The size of the nanoparticles is in the range from 7 to 30 nm.

Example V6

The incorporation of tetramethylorthosilicate into a crosslinked polyester film

A crosslinked polyester film sample was immersed in a solution containing 20.3 wt.% (25 vol.%) Anhydrous methanol and 79.7 wt.% (75 vol.%) Tetramethylorthosilicate (TMOS) for two hours. The film was removed from the methanol / TMOS mixture solution and placed in a 14% aqueous solution of ammonium hydroxide for two hours. The film is washed with water for 15 minutes and dried at room temperature for 17 hours. Silica in the form of particles is introduced into the polymer phase. TEM data show that the size of the nanoparticles is in the range from 7 to 300 nm.

Example V7

Introduction of titanium bis (ethyl acetoacetato) diisopropoxide in ethyl acetate

The thermosetting polyurethane of Example A was immersed in a solution containing 80.1 wt.% Anhydrous ethyl acetate and 19.9 wt.% Bis (ethylacetoacetato) titanium diisopropoxide for 24 hours. Polyurethane is removed from a solution of a mixture of ethyl acetate / bis (ethylacetoacetato) diisopropoxide titanium and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. The particulate titanium oxide phase is introduced into the polyurethane phase. TEM data show that the size of the nanoparticles is in the range from 5 to 200 nm.

Example V8

The introduction of zirconium (IV) acetylacetonate in ethyl acetate

The thermosetting polyurethane of Example A was immersed in a solution containing 91.2 wt.% Anhydrous ethyl acetate and 8.8 wt.% Zirconium (IV) acetylacetonate for 24 hours. Polyurethane is removed from a solution of a mixture of ethyl acetate / acetylacetonate zirconium (IV) and placed in a 14% aqueous solution of ammonium hydroxide for four hours. The polyurethane is washed with water and placed in an oven at 143 ° C for four hours. The particulate zirconia phase is introduced into the polyurethane phase.

Example W

Synthesis of Acrylsilane Polymers

For each of Examples AC shown in Table 23, the reaction flask was equipped with a stirrer, thermocouple, nitrogen inlet, and a refrigerator. Charge A is then added and stirred at reflux temperature (75-80 ° C.) under nitrogen. While refluxing ethanol, charge B and charge C were added simultaneously for three hours. The reaction mixture was refluxed for two hours. Then add loading D for 30 minutes. The reaction mixture was refluxed for two hours and then cooled to 30 ° C.

Table 31 Example A Example B Example C Download A (weight in grams) Ethanol SDA 40B ¹ 360.1 752.8 1440.2 Loading B (weight in grams) Methyl methacrylate 12.8 41.8 137.9 Acrylic acid 8.7 18.1 34.6 Silquest A-174 ² 101,4 211.9 405.4 2-hydroxyethyl methacrylate 14.5 0.3 0.64 n-butyl acrylate 0.2 0.3 0.64 Acrylamide 7.2 - - Sartomer SR 355 ³ - 30.3 - Ethanol SDA 40B 155.7 325.5 622.6 Download C (weight in grams) Vazo 67 ⁴ 6.1 12.8 24.5 Ethanol SDA 40B 76.7 160,4 306.8 Loading D (weight in grams) Vazo 67 1,5 2.1 6.1 Ethanol SDA 40B 9.1 18.9 36,2 % Solids 17.9 19.5 19.1 Acid number (100% resin solids) 51.96 45.64 45.03 Mn - 3021 ⁵ 5810 ¹ Denatured ethyl alcohol, degree 200, Archer Daniel Midland Co.
² gamma-methacryloxypropyltrimethoxysilane, GE silicones.
³ Ditrimethylol propane tetraacrylate, Sartomer Company Inc.
⁴ 2,2'-Azobis (2-methylbutyronitrile), EI DuPont de Nemours & Co., Inc.
⁵ Mn soluble portion; the polymer does not completely dissolve in tetrahydrofuran.

Example W1

The acryl silane resin of Example A (8.5 g) was mixed with polyvinylpyrrolidone (0.1 g) and water (1.5 g). The formulation was stored at room temperature for 225 minutes. Part of the resulting solution is loaded into a 10-ml syringe and released through a syringe pump at a speed of 1.6 ml / h into the multi-channel mouthpiece described in example 1. Electroforming conditions are described in example 1. Nanofibers in the form of a tape having a thickness of 100-200 nm and a width of 1200-5000 nm, is collected on crushed aluminum foil and characterized by optical microscopy and scanning electron microscopy. A nanofiber sample was dried in an oven at 110 ° C. for two hours. No measurable weight loss is observed. This indicates that the nanofibers are completely crosslinked.

Examples W2 and W3

Transparent composite products containing a polyurethane matrix and electroformed fibers of example 1, are obtained as follows.

In the case of each of examples 2 and 3 (see table 32 below), the reaction vessel was equipped with a stirrer, thermocouple, nitrogen inlet, receiver, and vacuum pump. Then, load A is added, stirred while heating to 80-100 ° C in vacuum and incubated for 1 hour. The reaction mixture is cooled to 80 ° C, the vacuum is removed and load B is added to the reaction vessel. Then the reaction mixture is heated to 80 ° C in vacuum and an exothermic reaction is carried out with increasing temperature to 110-120 ° C. The reaction mixture is then poured between two 5 × 5 × 3/16 '' float glass plates which are equipped with seals on three sides and held together by clamps. Both glass plates have a silane lubricant deposited on their surface, which are in contact with electroformed fibers and polyurethane. The fibers are formed on top of the processed plates before being assembled into a casting cell. The casting cell is assembled with an electroformed fiber coated with a plate on the inside of the casting cell. The space between the plates is approximately three sixteen inches. The casting cell is preheated before casting to a temperature of approximately 120 ° C. After casting, the assemblies are cured for 24 hours at 120 ° C and then 16 hours at 143 ° C. After curing, the cells are subjected to a two-hour cycle of gradual cooling from 143 ° C to 45 ° C, leaving them in the oven. The cells are removed from the furnace and the glass plates are separated from the composite product.

Polyurethane examples 2 and 3

Table 32 Download A (weight in grams) Example 2 Example 3 1,4-butanediol 31.54 - 1,10-Decanediol - 61.00 Trimethylolpropane 13.41 13.41 Loading B (weight in grams) DESMODUR W ¹ 131.00 131.00 ¹ bis (4-Isocyanatocyclohexyl) methane from Bayer Material Science.

Each composite product is tested for scratch resistance by subjecting it to scratching by longitudinally scratching the surface using loaded sandpaper for ten double friction using an Atlas ATCC Scratch Tester, Model CM-5 Scratch Hardness Tester, Model CM-5 (Atlas Electrical Devices Company, Chicago , Illinois). Used sandpaper sheets is 9 microns skins 3M 281Q WETORDRY ^TM PRODUCTION ^TM, which is commercially available from 3M Company, St. Poul, Minnesota.

At the end of the scratch hardness test using a Crockmeter using a 9 μm abrasive, an increase in the average surface roughness of the scratched area is measured using an optical profilometer. The surface of the scratched area is scanned perpendicular to the direction of scratching using a Crockmeter; that is, across the scratches. An identical scan is obtained on a non-scratched portion to measure the average surface roughness of the original product. The change in average surface roughness for each product is calculated by subtracting the average roughness of the scratched surface from the average roughness of the scratched surface. Transparent products without nanofibers are compared with transparent composite products containing the electroformed fibers of Example 3.

In addition, for comparison purposes, a composite product is obtained as a whole as described in example 3, but in this case polyvinylidene fluoride (KYNAR) and nylon 6 fibers are electroformed and placed instead of the fibers of example 3. Composite products are evaluated for scratch resistance as described above. The results are presented below in table 33.

Table 33 Example Electroformed Fiber Change in average surface roughness
(nm) The control No 74.54 Example 4 Example 3 6.93 Example 4 (repeat) Example 3 -7.28 Control (repeat) No 81.48 Example 5 Example 3 -4.91 Comparative Kynar 90.2 Comparative Nylon 6 66.96

The results presented in table 33 illustrate the improvement in scratch resistance that is provided by electroformed acrylic silane fibers.

Example X

Powder example

In a dry glass container, 1,4-butanediol (5.47 g, 0.122 equivalents) and 4.4'-methylene bis (cyclohexylisocyanate) are mixed together (DESMODUR W, Bayer Corporation; equivalent weight NCO 131; 14.52 g, 0.111 equivalent). One drop of dibutyltin dilaurate is added. The turbid mixture heats up spontaneously and becomes transparent. The mixture was placed in an oven at 120 ° C. for 6 hours.

A portion weighing 1.88 g of the obtained glassy solid polyurethane was dissolved in 5.23 g of M-Pyrol while boiling on a hot plate. Similarly, 3.68 g of M-Pyrol was dissolved in the trimer of isophorondiisocyanate (0.23 g). Two solutions are mixed in an aluminum cup and fired at 145 ° C for 35 minutes. The resulting film is transparent, dense and solid. Rubbing with methyl ethyl ketone does not soften the film or does not cause it to become sticky, which indicates its complete crosslinking.

Example Y

Liquid incorporation of an inorganic precursor into urethane resulting from in situ nanoparticles

A sample of urethane plastic is prepared as follows. Dimethyldichlorosilane is applied by vapor deposition on the surface of two pieces of tempered glass and the excess is washed with isopropanol. A rubber gasket (3/16 '' diameter) is placed between two pieces of glass and the pieces of glass are fixed together so that one end of the mold is open. The prepolymer is prepared by heating 504 g of 1,10-decanediol (3.55 mol, 0.7 equivalents) and 111 g of trimethylolpropane (0.83 mol, 0.3 equivalents) to 120 ° C. under vacuum in a three-necked round-bottom flask, where it is held 30 minutes. The contents of the flask were cooled to 80 ° C and 1084 g of dicyclohexylmethanediisocyanate (4.14 mol, 1 equivalent) was added. The exothermic reaction gives a temperature increase of up to 105 ° C, and the solution is poured into the open end of the glass form. The mold is placed in an oven at 120 ° C. for 24 hours and at 143 ° C. for 16 hours. The temperature was lowered to 43 ° C. over one hour, and the mold was removed from the oven. The mold is taken apart to extract the casting of the part from urethane plastic.

In a closed container, a solution is prepared containing 75% vol. tetramethylorthosilicate (TMOS) and 25% vol. methanol. A sample of urethane plastic is placed in a closed container and the container is washed with dry nitrogen. The urethane plastic is soaked in a TMOC / methanol solution for 4 or 24 hours. Urethane plastic is removed and immersed in: 1) water for 72 hours; 2) 2 M HCl for one hour and water for one hour; or 3) 15% solution (v / v) NH ₄ OH in water for one hour and water for one hour. Then the samples are annealed at 143 ° C for 4 hours. Soaking by immersion leads to hydrolysis and condensation of a liquid inorganic precursor (TMOS), which is embedded in plastic. Each soaking leads to nanoparticles of different sizes, and these particles are located in the plastic at different depths.

A person skilled in the art will understand that in the embodiments of the invention described above, changes can be made without deviating from the scope of the claimed concept. Thus, it is understood that the invention is not limited to the specific options described, but is intended to encompass modifications that are within the spirit and scope of the invention as defined in the claims.

Claims (37)

1. Polyurethane, which is a reaction product of components, including:
(a) about 1 equivalent of at least one polyisocyanate;
(b) from about 0.05 to about 0.9 equivalents of at least one branched polyol containing from 3 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) from about 0.1 to about 0.95 equivalents of at least one diol containing from 2 to 18 carbon atoms;
where the specified reaction product contains less than about 10 wt.% complex polyester polyol and / or simple polyether polyol, and, when mixed, the reaction components are maintained at a reaction temperature of at least about 100 ° C for at least about 10 minutes . 2. The polyurethane according to claim 1, where the polyisocyanate is selected from the group comprising diisocyanates, triisocyanates, their dimers, trimers and mixtures. 3. The polyurethane according to claim 2, where the polyisocyanate is a diisocyanate selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,3-methane diisocyanate, non-diene 6-hexamethylene triisocyanate, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, trimethylhexanediisocyanate, trimethylhexamethylene diisocyanate, 2,2'-dimethylpentane-diisocyanate, 2,2,4-trimethylhexanediisocyanate, 2,4,4 -trimethylhexamethylenediisocyanate, 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,5,7-trimethyl-1,8-diisocyanato-5- (isocyanatomethyl) octane, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, methyl ester of lysinediisocyanate 4,4'-methylene bis (cyclohexyl isocyanate), 4,4'-isopropylidene bis (cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate, 4,4'-dicyclohexyl methanediisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, meta-tetramethylsilylene diisocyanate, diphenylmethanediisocyanate, diphenylisopropylidene diisocyanate, diphenylenediisocyanate, butenediisocyanate at, 1,3-butadiene-1,4-diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl) -2,2-propane, bis (isocyanatocyclohexyl) ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] heptane, 2- isocyanato ethyl 3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) bicyclo [2.2. 1] heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane, α, α'-xyldiisocyanate, bis (isocyanatoethyl) benzene, α, α, α ', α'-tetramethylxylene diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesanate 2,5-di (isocyanatomethyl) furan, α, α'-xyldiisocyan , bis (isocyanatoethyl) benzene, α, α, α ', α'-tetramethylxyl diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, bis (isocyanato-butyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl ) diphenyl ether, bis (isocyanatoethyl) phthalate, 2,5-di (isocyanatomethyl) furan diisocyanate of diphenyl ether, bis (isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl ether) -1,3-propylene glycol, benzophenone diazodiisodiocyanediisodiocyanediisodiocyanated dimers, trimers and mixtures. 4. The polyurethane according to claim 3, where the diisocyanate is 4,4'-methylene bis (cyclohexyl isocyanate) or trans, the trans isomer of 4,4'-methylene bis (cyclohexyl isocyanate). 5. The polyurethane according to claim 2, where the polyisocyanate is a trimer of hexamethylene diisocyanate. 6. The polyurethane according to claim 2, where the polyisocyanate is a mixture of a dimer of hexamethylene diisocyanate and a trimer of hexamethylene diisocyanate. 7. The polyurethane according to claim 1, where the polyisocyanate is selected from the group comprising aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, their dimers and trimers, and mixtures thereof. 8. The polyurethane according to claim 1, where the branched polyol has three hydroxyl groups. 9. The polyurethane according to claim 1, wherein the branched polyol is selected from the group consisting of glycerol, tetramethylolmethane, trimethylol ethane, trimethylol propane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, their alkoxylated derivatives and mixtures thereof. 10. The polyurethane according to claim 9, where the branched polyol is trimethylolpropane. 11. The polyurethane according to claim 1, where the amount of branched polyol used to form the polyurethane is from about 0.3 to about 0.9 equivalent. 12. The polyurethane according to claim 1, where the diol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, decanediol, , beckons, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzene dimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene bis (2-hydroxyethyl) terephthalate, 1,4-bis (hydroxyethyl) piperazine, N, N'-n'-bis (2-hydroxyethyl) oxamide and mixtures thereof. 13. The polyurethane according to item 12, where the diol is butanediol. 14. The polyurethane according to item 12, where the diol is pentanediol. 15. The polyurethane according to claim 1, where the amount of diol used to form the polyurethane is from about 0.3 to about 0.7 equivalent. 16. The polyurethane according to claim 1, where the reaction product of the components includes less than about 0.1 equivalent polyester polyol or polyether polyol. 17. Polyurethane according to claim 1, wherein the reaction product of components further comprises one or more polyurethane polyols, acrylamides, polyvinyl alcohols, acrylate having a hydroxyl functionality, hydroxyl functionality methacrylates, allylic alcohols, digidroksioksamidov, digidroksiamidov, digidroksipiperidinov, digidroksiftalatov, digidroksietilgidrohinonov and mixtures thereof. 18. The polyurethane according to claim 1, where the reaction product of the components contains less than about 10 wt.% Amine curing agent. 19. The polyurethane according to claim 1, where the reaction product of the components contains less than about 5 wt.% Thiol groups. 20. The polyurethane according to claim 1, where the polyurethane has a hard segments content of from about 10 to about 100 wt.%. 21. The polyurethane according to claim 1, where the polyurethane has a urethane content of from about 20 to about 40 wt.%. 22. The polyurethane according to claim 1, where the polyurethane has a cyclic group content of from about 10 to 80 wt.%. 23. The polyurethane according to claim 1, where the polyurethane has a molecular weight crosslinking of at least about 500 g / mol. 24. The polyurethane according to claim 1, where the reaction components are maintained at a temperature of at least about 110 ° C for at least about 10 minutes 25. The polyurethane according to claim 1, where the reaction components are kept at a temperature of at least about 100 ° C for at least about 20 minutes 26. Polyurethane, which is a reaction product of components consisting of:
(a) approximately 1 equivalent of 4,4'-methylene bis (cyclohexyl isocyanate);
(b) from about 0.3 to about 0.5 equivalent of trimethylolpropane; and
(c) from about 0.3 to about 0.7 equivalents of 1,10-dodecanediol, 1,4-butanediol or 1,5-pentanediol,
where, when mixed, the reaction components are held at a reaction temperature of at least about 100 ° C. for at least about 10 minutes. 27. A product made of polyurethane according to claim 1. 28. The product according to item 27, where the product has a shock resistance according to Gardner, at least about 65 inch-pounds (7.3 joules) in accordance with ASTM-D 5420-04. 29. The product according to item 27, where the product has a toughness Dynatup of at least about 35 J. 30. The product according to item 27, where the product has a coefficient of resistance to crack propagation, at least about 1000 pounds / inch ^3/2 . 31. The product according to item 27, where the product has a resistance to abrasion according to Taber (100 cycles) less than approximately 45% turbidity. 32. The product according to item 27, where the product has a resistance to cracking under stress in an organic solvent of at least about 1000 psi. inch tensile load. 33. The product according to item 27, where the product is a molded product. 34. The product according to item 27, where the product is selected from the group including transparent products, optical products, photochromic products, ballistic resistant products and glazing. 35. An article made of polyurethane containing a reaction product of components including:
(a) about 1 equivalent of at least one polyisocyanate;
(b) from about 0.1 to about 0.9 equivalents of at least one branched polyol containing from 3 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) from about 0.1 to about 0.9 equivalents of at least one diol containing from 2 to 18 carbon atoms;
where the specified reaction product contains less than about 10 wt.% complex polyester polyol and / or simple polyether polyol, and the product has a Gardner impact resistance of at least about 200 inch-pounds (23 J) in accordance with ASTM-D 5420-04 and, when mixed, the reaction components are held at a reaction temperature of at least about 100 ° C. for at least about 10 minutes. 36. A laminate comprising:
(a) at least one layer of polyurethane according to claim 1; and
(b) at least one layer of a base selected from the group consisting of paper, glass, ceramics, wood, stone, fabric, metal or organic polymeric material and compositions thereof. 37. A coating composition comprising a polyurethane according to claim 1.

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