KR20160031009A - Isocyanate prepolymer composition and crosslinked polyurethane prepared therefrom - Google Patents

Abstract

An isocyanate prepolymer composition and a crosslinked thermoplastic polyurethane composition, preferably a composition in fiber form, are disclosed. The prepolymer composition and the process for producing the crosslinked thermoplastic polyurethane are also disclosed. Both the isocyanate prepolymer composition and the crosslinked thermoplastic polyurethane exhibit improved properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isocyanate prepolymer composition and an isocyanate prepolymer composition and a crosslinked polyurethane prepared from the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an isocyanate prepolymer composition and a crosslinked thermoplastic polyurethane composition prepared therefrom, particularly a composition in the form of a melt-spun elastic fiber, and a process for preparing the isocyanate prepolymer composition and the crosslinked polyurethane composition .

Thermoplastic polyurethanes (TPU) have been identified for many industrial applications due to their excellent mechanical properties and inexpensive processing. By varying the composition of the TPU, a wide variety of properties can be achieved. It is known that in order to improve the characteristic profile of the TPU, a cross linker can be introduced into the TPU to induce an increase in strength.

WO 2008/116801 A1 discloses a process for the reaction of a compound having isocyanate groups with a thermoplastic polyurethane. EP 1 078 944 relates to the synthesis of thermoplastic polyurethanes which additionally use isocyanates having three reactive isocyanate groups with uretonimine structure. WO 2005/054322 discloses a process for reacting an isocyanate containing three isocyanate groups with a thermoplastic polyurethane. The reaction of a thermoplastic polyurethane, preferably a molten thermoplastic polyurethane, with a compound having an isocyanate group is referred to as prepolymer crosslinking and is described in US 4261946, US 4347338, DE 41 15 508 A1, DE 44 12 329A1, EP 922 719A1, GB 2347933 , US 6142189, EP 1 158 011 A1, EP 1 692 203 A1 and WO 2005/053 938.

Conventional crosslinked TPUs generally comprise the reaction product of an isocyanate prepolymer, a thermoplastic polyurethane, which may be prepared in the reaction of a diisocyanate with a polyol. CN 101205289A discloses a process for preparing an isocyanate prepolymer having an average isocyanate functionality (Fn)> 2 by adding a triol or a tetraol such as glycerol. It should be noted that this process produces a high viscosity isocyanate prepolymer which has been found to be fatal to the properties of the prepolymer and crosslinked TPU prepared therefrom, such as processability and applicability. EP 0 922 719 A1 discloses an isocyanate prepolymer having functionality = 2, and by using such an isocyanate prepolymer, the crosslinked TPU exhibited a higher HDT temperature.

It was an object of the present invention to develop functionalities > 2 prepolymer compositions with improved properties, especially reduced viscosity. Accordingly, the present invention provides an isocyanate prepolymer composition comprising:

Isocyanate prepolymer;

Polymethylene polyphenyl polyisocyanate (PMDI), more preferably PMDI, having the chemical structure shown below is a mixture of compounds having the chemical formula as shown below (also referred to as PMDI or PMDI mixture)

; 및 경우에 따라,

; And, optionally,

Plasticizer.

The present invention further provides a process for preparing an isocyanate prepolymer composition comprising the step of mixing the following components:

Isocyanate prepolymer;

PMDI having the chemical structure shown below, more preferably PMDI, is a mixture of compounds having the chemical formulas shown below

; 및 경우에 따라,

; And, optionally,

Plasticizer.

In a preferred embodiment, if a plasticizer is present in the composition, the isocyanate prepolymer is first mixed with the plasticizer, and then the resulting mixture is mixed with the PMDI, and more preferably with the PMDI mixture as set forth above.

It is another object of the present invention to provide crosslinked thermoplastic polyurethane compositions having improved properties, especially high temperature resistance. The present invention provides a crosslinked thermoplastic polyurethane composition comprising the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

In a preferred embodiment, the crosslinked thermoplastic polyurethane composition is in the form of a melt-spun elastomeric fiber.

Additionally, the present invention provides a process for preparing a crosslinked thermoplastic polyurethane composition comprising reacting the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

The present invention additionally provides uses of PMDI and / or plasticizers in the preparation of isocyanate prepolymer compositions or crosslinked thermoplastic polyurethane compositions.

In the present invention, most preferably, the isocyanate prepolymer is selected from the group consisting of diphenylmethane 4,4'-diisocyanate, and / or diphenylmethane 2,2'-diisocyanate, and / or diphenylmethane 2,4'-diisocyanate (MDI) and a polyester polyol based on adipic acid, 2-methyl-1,3-propanediol and trimethylol propane.

According to the present invention, the isocyanate prepolymer composition exhibits a substantially reduced viscosity. Crosslinked thermoplastic polyurethane compositions also exhibit improved high temperature resistance. The product has a general high strength of the TPU combined with a lower tension set and higher use temperature, which is important in the case of elastic fibers.

For purposes of the present invention, all operations and measurements are performed at room temperature and at atmospheric pressure, unless otherwise indicated.

For purposes of the present invention, "isocyanate prepolymer composition" refers to a mixture or blend of an isocyanate prepolymer, PMDI and, where appropriate, a plasticizer.

For purposes of the present invention, "crosslinked thermoplastic polyurethane composition" refers to a product prepared by reacting a thermoplastic polyurethane with an isocyanate prepolymer composition according to the present invention, regardless of the thermoplastic or thermosetting properties of the resulting product.

For purposes of the present invention, unless otherwise indicated, the molecular weight of the polymer material is determined by gel permeation chromatography (GPC) according to DIN 55672-1: 2007 using tetrahydrofuran as the eluent and PMMA as the calibration standard Refers to the average molecular weight.

The isocyanate prepolymer composition of the present invention

Isocyanate prepolymer;

PMDI having a chemical structure as shown below, more preferably PMDI, is a mixture of compounds having the formula as shown below

; 및 경우에 따라,

; And, optionally,

And a plasticizer.

In preferred embodiments, the weight ratio of isocyanate prepolymer to plasticizer can range from about 1: 0.2 to 1: 0.05 and the weight ratio of isocyanate prepolymer to PMDI is from about 1: 0.1 to about 1: 5, preferably from about 1: 0.2 To about 1: 3, more preferably from about 1: 0.3 to about 1: 2, more preferably from about 1: 0.3 to about 1: 1.5, and most preferably from about 1: 0.33 to 1: have.

The crosslinked thermoplastic polyurethane composition of the present invention comprises the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

In one particular embodiment, the crosslinked thermoplastic polyurethane composition of the present invention comprises the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And

Additional substances.

In one particular embodiment, the crosslinked thermoplastic polyurethane composition of the present invention consists essentially of the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

In the context of this embodiment, "consisting essentially of" is meant to include more than 50 wt-%, more preferably more than 75 wt-%, more preferably more than 90 wt-%, most preferably more than 97 wt-% Means that the thermoplastic polyurethane composition is derived from the above components.

In a further particular embodiment, the crosslinked thermoplastic polyurethane composition of the invention consists of the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

In a preferred embodiment, the crosslinked thermoplastic polyurethane composition is in the form of a melt-spun elastomeric fiber. The cross-section of the fibers is circular, oval, triangular, square, or Y-shaped depending on the design of the spinneret in the preferred embodiments. In other preferred embodiments, the fibers are multi-filaments. The line density of the fibers is 15 denier to 1000 denier, preferably 15 denier to 70 denier, and most preferably 20 denier to 40 denier. A denier is a unit for describing the line density of a fiber, and a 20 denier means that a 9,000 m long fiber has a weight of 20 g.

Additionally, the present invention provides a process for preparing a crosslinked thermoplastic polyurethane composition comprising reacting the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And, optionally,

Additional substances.

In one particular embodiment, the process for preparing a crosslinked thermoplastic polyurethane composition of the present invention comprises reacting the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And

Additional substances.

In preferred embodiments, the weight ratio of isocyanate prepolymer composition to thermoplastic polyurethane composition is from about 1: 0.01 to 1: 0.5, preferably from about 1: 0.02 to 1: 0.4, more preferably from about 1: 0.04 to 1: 0.2 , And most preferably from about 1: 0.05 to 1: 0.15.

In a preferred embodiment, if a plasticizer is present in the composition, the isocyanate prepolymer is first blended with the plasticizer, which is referred to as the product mixture or mixture 1, and in the second step the product mixture (mixture 1) Is mixed with the PMDI mixture, which produces mixture 2, which is then added to and mixed with mixture 2 in a third step to produce mixture 3. In an even more preferred embodiment, the plasticizer is mixed with the starting material of the isocyanate prepolymer.

In the present invention, most preferably, the isocyanate prepolymer is selected from the group consisting of diphenylmethane 4,4'-diisocyanate, and / or diphenylmethane 2,2'-diisocyanate, and / or diphenylmethane 2,4'-diisocyanate (MDI) and a polyester polyol based on adipic acid, 2-methyl-1,3-propanediol and trimethylol propane.

The components and processing will be described below:

One preferred embodiment (1) of the present invention is an isocyanate prepolymer composition comprising:

Isocyanate prepolymer;

Polymethylene polyphenyl polyisocyanate (PMDI), more preferably PMDI, having the chemical structure shown below is a mixture of compounds having the chemical formulas as shown below:

; And optionally a plasticizer.

Another preferred embodiment (2) of the present invention is an isocyanate prepolymer composition according to embodiment (1) wherein the isocyanate prepolymer is reactive with (a) an isocyanate and (b) isocyanate and has a And a compound having a number average molecular weight.

Another preferred embodiment (3) is an isocyanate prepolymer composition according to embodiment (1) or (2) wherein the isocyanate prepolymer is diphenylmethane 4,4'-diisocyanate and / or diphenylmethane 2,2'- The reaction product of diisocyanate and / or diphenylmethane 2,4'-diisocyanate (MDI) with a polyester polyol based on adipic acid, 2-methyl-1,3-propanediol and / or trimethylolpropane , And the molar ratio of the polyester polyol to the diisocyanate is 1: 1 to 1: 3, preferably 1: 1.5 to 1: 2.5, more preferably 1: 2.

Another preferred embodiment (4) is an isocyanate prepolymer composition according to embodiment (1), (2) or (3), wherein the isocyanate prepolymer comprises diphenylmethane 4,4'- diisocyanate, adipic acid, 2- Methyl-1,3-propanediol and trimethylol propane, and the ratio of 2-methyl-1,3-propanediol and trimethylol propane to the polyester polyol has an average functionality of > 2, 2.1 to 3, more preferably 2.1 to 2.7, more preferably 2.2 to 2.5 and most preferably 2.3 to 2.5.

Another preferred embodiment (5) is an isocyanate prepolymer composition according to any one of embodiments (1), (2), (3) and (4) wherein the PMDI, more preferably the PMDI mixture, To 6, preferably from 2 to 4, more preferably from 2.5 to 3.

Another preferred embodiment (6) is an isocyanate prepolymer composition according to any one of embodiments (1), (2), (3), (4) and (5) wherein PMDI, Lupranate® M20S, M20R, and mixtures thereof.

Another preferred embodiment (7) is an isocyanate prepolymer composition according to any one of embodiments (1), (2), (3), (4), (5) and (6) Having an isocyanate functionality of greater than 2, preferably from 2.1 to 3, more preferably from 2.1 to 2.7, preferably from 2.2 to 2.7 and most preferably from 2.3 to 2.5.

Process (1) for producing an isocyanate prepolymer composition according to any one of embodiments (1), (2), (3), (4), (5), (6) PMDI, preferably a PMDI mixture, and optionally a plasticizer.

Another preferred method (2) for the preparation of the isocyanate prepolymer composition comprises mixing the PMDI, preferably the PMDI mixture, and / or the plasticizer with the starting material of the isocyanate prepolymer, or if an isocyanate prepolymer is present in the composition, First, a method of mixing with a plasticizer, and then mixing with PMDI and preferably with a PPMDI mixture (1).

Another preferred embodiment (10) of the present invention is a crosslinked thermoplastic polyurethane composition essentially comprising the reaction product of the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to any one of claims 1 to 7; And, optionally,

Additional substances.

Yet another preferred embodiment (11) is a crosslinked thermoplastic polyurethane composition according to embodiment (10) in the form of a fiber, more preferably such fibers are melt spinning, even more preferably it is also elastic, It is a spun elastic fiber.

A preferred method (12) for the preparation of crosslinked thermoplastic polyurethane compositions according to embodiment (10) or (11) comprises reacting the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to any one of claims 1 to 7; And, optionally,

Additional substances.

Another preferred method (13) for the production of cross-linked thermoplastic polyurethane compositions according to embodiment (10) or (11) comprises contacting PMDI and / or plasticizer with thermoplastic polyurethane, isocyanate prepolymer and / or isocyanate prepolymer and thermoplastic poly To the mixture of urethane (12).

Another preferred method (14) for the preparation of crosslinked thermoplastic polyurethane compositions according to embodiment (10) or (11) comprises mixing PMDI and / or a plasticizer with the starting material of an isocyanate prepolymer, If present, the isocyanate prepolymer is first mixed with a plasticizer, and then mixed with PMDI (12) or (13). The starting material is used to define all the materials used in prepolymer production.

Another preferred method (15) for the production of cross-linked thermoplastic polyurethanes according to embodiment (10) or (11) comprises the following steps:

(1) melting the thermoplastic polyurethane at a temperature of 180 ° C to 220 ° C in an extruder;

(2) adding an isocyanate prepolymer composition according to any one of the embodiments (1) to (7) to the molten thermoplastic polyurethane and mixing the resulting mixture to form a melt; And

(3) Extruding the melt through a spinneret heated at 190 캜 to 230 캜 to obtain melt-spun elastomeric fibers.

Another preferred method 16 for the production of a crosslinked thermoplastic polyurethane composition according to embodiment (10) or (11) is a method (15) which further comprises the following steps:

(4) spraying a finish oil onto the fibers, wherein the finish oil is preferably a mineral oil and / or a silicone oil;

(5) winding up the fibers through a roller at a linear velocity of 100 to 1000 m / min; And

(6) Storing the fibers at 80 DEG C for at least 15 hours.

Another part of the present invention is a process for the preparation of an isocyanate prepolymer composition as defined herein or a crosslinked thermoplastic polyurethane composition as defined in the present disclosure, wherein the PMDI as defined herein and / Lt; / RTI >

Thermoplastic polyurethane composition

In the present invention, the thermoplastic polyurethane comprises the following components:

(a) at least one organic diisocyanate,

(b) at least one compound that is reactive toward isocyanate,

(c) at least one chain extender, preferably having a molecular weight of from 60 g / mol to 499 g / mol, and

(d) optionally at least one catalyst, and / or

(e) optionally at least one adjuvant, and / or

(f) optionally at least one additive.

The thermoplastic polyurethane composition has a number average molecular weight of from 8 * 10 ⁴ g / mol to 1.8 * 10 ⁵ g / mol, more preferably from 1.0 * 10 ⁵ g / mol to 1.5 * 10 ⁵ g / mol.

The components (a), (b), (c) and optional components (d), (e) and (f) used in the present invention are exemplarily described below.

Isocyanate

Suitable and preferred organic diisocyanates (a) are conventional aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates. Preferred examples thereof include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, butylene Diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (Isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane 1,4- diisocyanate, 1-methylcyclohexane 2,4 - and / or 2,6-diisocyanate, dicyclohexylmethane 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI), diphenylmethane 2,2'-, 2 , 4'- and / or 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl diphenyl diisocyanate, 1,2-diphenyl ethane diisocyanate , Phenylene diisocyanate, and any combination thereof. The diisocyanate is a single diisocyanate or a mixture of diisocyanates.

Diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), and dicyclohexylmethane 4,4'-, 2,4'- and / or 2,2 '- diisocyanate (H12MDI) are each preferred embodiments. Diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate are particularly preferred.

In a particularly preferred embodiment, the organic diisocyanate (a) comprises at least 90% by weight, more preferably at least 95% by weight, more preferably at least 98% by weight of 4,4'-diphenylmethane diisocyanate '-MDI), with the remainder being other diisocyanates, preferably 2,2'- and / or 2,4'-diphenylmethane diisocyanate.

Polyol

The isocyanate-reactive compound (b) is preferably a polyhydric alcohol, a polyesterol (i.e., polyesterpolyol), a polyetherol (i.e., a polyetherpolyol), and / or a polycarbonate diol, "Polyol" is also commonly used. These polyols have a number average molecular weight (Mn) of 0.5 kg / mol to 8 kg / mol, preferably 0.6 kg / mol to 5 kg / mol, very preferably 0.8 kg / mol to 3 kg / mol, / mol to 2 kg / mol.

These polyols additionally preferably have only a primary hydroxyl group. The polyol is particularly preferably a linear hydroxyl-terminated polyol. Due to the method of preparation, these polyols often contain small amounts of non-linear compounds. They are therefore also often referred to as "essentially linear polyols ".

The polyol is a single polyol or a mixture of polyols. In another preferred embodiment, the polyol is a mixture of two or more polyols. In one preferred embodiment, it is a mixture of polyester polyols and other polyols such as polyester polyols, polyether polyols and / or polycarbonate diols as compound (b). More preferred are mixtures of polyester polyols and at least one polyether polyol.

In the case of a mixture of polyols, at least one polyester polyol is present in an amount of more than 40% by weight, preferably more than 60% by weight, more preferably more than 80% by weight, and most preferably 90% % ≪ / RTI >

In the present invention, polyether diols, polyester diols, and polycarbonate diols are known and commonly used in the production of TPU.

The polyester diols may be based on dicarboxylic acids having from 2 to 12 carbon atoms, preferably from 4 to 8 carbon atoms, which are generally known for the production of polyester diols and polyhydric alcohols.

Preferred examples of polyhydric alcohols are alkanediols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and dialkylene ether glycols such as diethylene glycol and dipropylene glycol. Further examples of polyhydric alcohols are 2,2-bis (hydroxymethyl) 1,3-propanediol and trimethylolpropane. Depending on the nature desired, the polyhydric alcohols may be used alone or in mixtures with one another, as appropriate. In order to keep the glass transition temperature Tg of the polyol very low, a polyester diol based on a branched diol, particularly preferably based on 3-methyl-1,5-pentanediol and 2-methyl- It may be advantageous to use. The polyester diols are particularly preferably based on at least two different diols, i.e. polyester diols prepared by condensation of a dicarboxylic acid with a mixture of at least two different diols. In a mixture of diols, if at least one of them is a branched diol, such as 2-methyl-1,3-propanediol, the amount of branched diol is greater than 40% by weight, More preferably more than 70% by weight, more preferably more than 90% by weight.

Preferred dicarboxylic acids are for example: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and preferably adipic acid and aromatic dicarboxylic acids such as phthalic acid, Isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as a mixture, for example in the form of a mixture of succinic acid, glutaric acid and adipic acid. Mixtures of aromatic and aliphatic dicarboxylic acids may also be used. In order to prepare the polyesterol, a corresponding dicarboxylic acid derivative instead of a dicarboxylic acid such as a dicarboxylic acid ester having 1 to 4 carbon atoms in an alcohol radical, a dicarboxylic acid anhydride or a dicarboxylic acid chloride May be advantageous. The polyester diols are particularly preferably based on adipic acid. In another embodiment, a polyester polyol based on? -Caprolactone is preferred.

Preferred polyester polyols have a number average molecular weight of from 0.5 to 3 kg / mol, preferably from 0.8 kg / mol to 2.5 kg / mol, more preferably from 1 kg / mol to 2 kg / mol, (Mn).

Suitable polyether polyols may be prepared by reacting one or more alkylene oxides having from 2 to 4 carbon atoms in an alkylene radical with a starting material molecule containing two active hydrogen atoms. Typical alkylene oxides are ethylene oxide, 1,2-propylene oxide, epichlorohydrin, and 1,2- and 2,3-butylene oxide. Ethylene oxide, and a mixture of 1,2-propylene oxide and ethylene oxide are preferably used. The alkylene oxides may be used individually, alternatingly in succession, or as a mixture. Typical starting material molecules are, for example, water, amino alcohols such as N-alkyldiethanolamines, and diols, preferably such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol . Mixtures of starting material molecules may also be used. Preferred polyether polyols include the hydroxyl group-containing polymerization product of tetrahydrofuran.

Preferably a hydroxyl group-containing polytetrahydrofuran, and a co-polyether polyol of 1,2-propylene oxide and ethylene oxide, wherein more than 50%, preferably 60 to 80% Primary hydroxyl group, and at least a portion of the ethylene oxide is a block at the terminal position).

Most preferred polyether polyols have a number average molecular weight ranging from 0.6 kg / mol to 3 kg / mol, preferably from 0.8 kg / mol to 2.5 kg / mol, more preferably from 1 kg / mol to 2 kg / Containing polytetrahydrofuran.

The preferred polyol is a mixture of at least one polyester polyol and at least one polyether polyol.

Examples of polyether polyols include, but are not limited to, those based on commonly known starting materials and conventional alkylene oxides.

The polyol according to the present invention can react with an isocyanate to produce an isocyanate prepolymer or can react with an isocyanate prepolymer to produce a TPU.

Preferred polyols used to react with isocyanates to produce isocyanate prepolymers have an average functionality of greater than 2, preferably from 2.1 to 3, more preferably from 2.1 to 2.7, and most preferably from 2.2 to 2.5. Suitable polyols for use in producing TPU by reaction with isocyanate prepolymers also preferably have an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, especially 2. The term " functionality "means the number of groups that react with the isocyanate under polymerization conditions.

Chain extender

As the chain extender (c), there may be mentioned generally known aliphatic, araliphatic, aromatic and / or alicyclic compounds having a molecular weight of 60 g / mol to 499 g / mol, preferably 60 g / mol to 400 g / mol Preferably bifunctional compounds such as diamines and / or alkanediols having from 2 to 10 carbon atoms in the alkylene radical, especially 1,2-ethylene diol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, and / or a dialkylene-, trialkylene-, tetraalkylene-, pentaalkylene-, hexaalkylene-, heptaalkyl-, and the like having 2 to 8 carbon atoms in the alkylene moiety Rhen-, octaalkylene-, nonalkylene- and / or decaalkylene-glycols, preferably corresponding oligo-propylene glycols and / or polypropylene glycols can be used. In preferred embodiments, a mixture of chain extenders is used. As the chain extender, 1,4-butanediol, 1,2-ethylene diol, 1,6-hexanediol or a combination thereof is preferable.

In a preferred embodiment, the chain extender (c) is used in an amount of from 2 to 20% by weight, preferably from 5 to 15% by weight, based on the total weight of components (a), (b) and (c).

The chain extender is a single chain extender, or a mixture of chain extenders.

catalyst

In particular, suitable catalysts (d) for promoting the reaction between the NCO group of the organic diisocyanate (a) and the polyol (b) and component (c) are well known in the art and include conventional tertiary amines such as triethylamine , Dimethylcyclohexylamine, N-methylmorpholine, 2- (dimethylaminoethoxy) ethanol, N, N'-dimethylpiperazine, diazabicyclo [2.2.2] octane, (III) acetylacetonate, tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or aliphatic carboxylic acids, such as, for example, titanium compounds such as titanium esters, bismuth carboxylic acid esters, zinc esters, iron compounds such as iron Dialkyltin salts such as dibutyltin diacetate, dibutyltin dilaurate, and the like. The oxidation state of bismuth in the bismuth salt is preferably 2 or 3, more preferably 3.

The preferred carboxylic acid of the bismuth carboxylic acid ester has 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms. Preferred examples of the bismuth salts are bismuth (III) -neodecanoate, bismuth-2-ethylhexanoate and bismuth-octanoate.

The catalyst, if used, is generally used in an amount of from 0.0001 to 0.1 part by weight per 100 parts by weight of polyol (b). Tin catalysts, especially tin dioctoate, are preferred.

Apart from the catalyst (d), usual adjuvants (e) and / or additives (f) can be added in addition to the components (a) to (c) if desired.

Stabilizers for surface active substances, flame retardants, nucleating agents, lubricant waxes, dyes, pigments, and stabilizers, such as oxidation, hydrolysis, light, heat or discoloration, may be mentioned as preferred examples, As the additive (f), inorganic and / or organic fillers and reinforcing materials can be mentioned as preferred examples. As hydrolysis inhibitors, oligomeric and / or polymeric aliphatic or aromatic carbodiimides are preferred. In order to stabilize the TPU of the present invention against aging, stabilizers are added to the TPU in the preferred embodiments. For the purposes of the present invention, stabilizers are additives that protect plastics or plastic mixtures from harmful environmental effects.

The catalyst is a single catalyst or a mixture of catalysts.

If the TPU of the present invention is exposed to thermal oxidative damage during use, antioxidants are added in the preferred embodiments. Phenolic antioxidants are preferred. Phenolic antioxidants such as Irganox 1010 from BASF are provided in the Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001, pages 98-107, pages 116 and 121. A phenolic antioxidant having a number average molecular weight of from 0.6 x 10 ³ g / mol to 2 x 10 ³ g / mol is preferred.

One example of a phenolic antioxidant that is preferably used is pentaerythrityl tetrakis (3- (3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) propionate) and 3,3 ' 1: 1 mixture of bis (3,5-di-tert-butyl-4-hydroxyphenyl) -n, n'-hexamethylene dibropionamide (Irganox® 1125, BASF).

The phenolic antioxidant is preferably used in a concentration of from 0.1 to 5% by weight, preferably from 0.1 to 2% by weight, especially from 0.5 to 1.5% by weight, based on the total weight of the TPU.

The TPU exposed to UV light is preferably additionally stabilized using a UV absorber. UV absorbers are generally known as molecules that absorb high energy UV light and dissipate energy. Typical UV absorbers used in the industry are, for example, in the group of cinnamic esters, diphenyl cyan acrylate, formamidine, benzylidene malonate, diaryl butadiene, triazine and benzotriazole. Examples of typical UV absorbers can be found in the Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001, pages 116-122.

In a preferred embodiment, the UV absorber has a number average molecular weight of more than 0.3 x 10 ³ g / mol, in particular more than 0.39 x 10 ³ g / mol. Furthermore, the UV absorber preferably used has a molecular weight of 5 x 10 ³ g / mol or less, particularly preferably 2 x 10 ³ g / mol or less.

A particularly useful UV absorber is benzotriazole. Examples of particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 328, Tinuvin® 571 and Tinuvin® 384 from BASF SE and also Eversorb®82 from Everlight Chemical. The UV absorber is preferably added in an amount of from 0.015% to 5% by weight, based on the total weight of the TPU, and is preferably from 0.15% to 2.0% by weight, especially from 0.25% to 0.5% By weight.

The UV stabilizers described above based on antioxidants and UV absorbers are often not sufficient to ensure good stability of the TPU against the deleterious effects of UV in some applications. In this case, hindered amine light stabilizers (HALS) may be added to the TPU in addition to antioxidants and UV absorbers. The activity of HALS compounds is based on their ability to form nitroxyl radicals that intervene in the oxidation mechanism of the polymer. HALS is a highly efficient UV stabilizer for most polymers.

HALS compounds are generally known and commercially available. Examples of commercially available HALS can be found in the Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pages 123-136. As the "hindered amine light stabilizer ", hindered amine light stabilizers having a number average molecular weight exceeding 0.5 kg / mol are preferable. Further, the molecular weight of the preferred HALS compound is 10 kg / mol or less, particularly preferably 5 kg / mol or less.

Particularly preferred "hindered amine light stabilizers" are bis (1,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, BASF SE), and 1-hydroxyethyl- Condensation product of 6,6-tetramethyl-4-hydroxypiperidine with succinic acid (Tinuvin® 622). The condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (when the titanium content of the product is <150 ppm, preferably <50 ppm, Tinuvin (R) 622) is very particularly preferred. The HALS compound is preferably used in a concentration of from 0.01 to 5% by weight, particularly preferably from 0.1 to 1% by weight, in particular from 0.15 to 0.3% by weight, based on the total weight of the TPU.

Particularly preferred UV stabilizers include mixtures of phenolic stabilizers, benzotriazole and HALS compounds in the preferred amounts described above.

Further details relating to the aforementioned adjuvants and additives can be found in the specialized literature, for example in the Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001.

A chain regulator having a number average molecular weight of 31 g / mol to 3 kg / mol may be used in addition to the components a), b) and c) and, if appropriate, d) and e). These chain modifiers are only compounds having one isocyanate-reactive functional group, such as monohydric alcohols, monofunctional amines and / or monofunctional polyols. This kind of chain control agent allows precise rheology to be set, especially in the case of TPU. The chain modifier may be used in an amount of generally 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of component b), and is included in component (c) in the definition of the term.

In order to control the hardness of the TPU, the component (b) and the chain extender (c) which are reactive toward isocyanate may vary within a relatively wide molar ratio range. It has been found useful when the molar ratio of the total of the component (b) to the chain extender (c) is from 10: 1 to 1:10, especially from 1: 1 to 1: 4, and the hardness of the TPU is increased &Lt; / RTI &gt;

The thermoplastic polyurethanes used as the base for the end product, also referred to as thermoplastic polyurethane compositions, also referred to as crosslinked polyurethanes, preferably have a Shore A hardness in accordance with DIN 53505 of generally less than 98 Shore A, more preferably less than 45 Shore A to 95 Shore A, even more preferably 60 Shore A to 90 Shore A, most preferably 75 Shore A to 90 Shore A.

Preferably, the thermoplastic polyurethane composition of the present invention has a density in the range of 1.0 g / cm3 to 1.3 g / cm3. The tensile strength of the TPU composition according to DIN 53504 exceeds 10 MPa, preferably above 15 MPa, particularly preferably above 20 MPa. The TPU compositions of the present invention have a wear loss generally in accordance with DIN 53516 of less than 150 psi, preferably less than 100 psi.

Generally, thermoplastic polyurethanes are prepared by reacting (a) an isocyanate with (b) a number average molecular weight (Mn) of 0.5 kg / mol to 10 kg / mol, preferably 0.5 kg / mol to 5 kg / mol, (C) a chain extending agent having a number average molecular weight (Mn) in the range from 0.05 kg / mol to 0.499 kg / mol and, if appropriate, (d) a catalyst and / (E) in the presence of customary additives.

The thermoplastic polyurethane can be prepared by two different processes, namely a "one-step" process and a "two-step" process.

In the one-step process, the raw materials of the thermoplastic polyurethane composition are mixed together continuously or batchwise by methods known in the art. The one-step process for the preparation of the TPU compositions of the present invention comprises reacting component (a) with component (b) and component (c) and optionally component (d) and / or component (e) To react with component (f) according to formula (I). Preferably, the reaction is carried out at a temperature in the range of 70 ° C to 280 ° C, more preferably 80 ° C to 250 ° C, even more preferably 80 ° C to 220 ° C.

In a two-step process, the thermoplastic polyurethane composition comprises (a) at least one compound reactive with isocyanate and (b) isocyanate, preferably at least one chain extender having a molecular weight of from 60 g / mol to 499 g / Lt; RTI ID = 0.0 &gt; NCO &lt; / RTI &gt; The NCO prepolymer refers to an intermediate product of an isocyanate polyaddition reaction with an excess of NCO groups. These prepolymers preferably have an NCO content of from 8 to 27% by weight, based on the weight of the prepolymer. In the second step, the NCO prepolymer will react in the presence of one or more compounds which are subsequently reactive with isocyanate, also referred to as (b) polyol, if appropriate, (d) catalyst and / or (e) conventional additives.

The thermoplastic polyurethanes prepared in the manner outlined above are thermoplastic, meaning that the molecules are not actually crosslinked. The thermoplastic polyurethane is therefore meltable. Such thermoplastic polyurethanes are generally produced in the form of granules, pellets, and the like. Heating and molding these thermoplastic polyurethanes will yield the final product.

The reaction for preparing the TPU composition of the present invention can be carried out at an ordinary index, preferably at an index of 0.6 to 1.2, more preferably at an index of 0.8 to 1.1. The index is defined as the molar ratio of the total isocyanate group of component (a) used in the reaction to the group reactive with the isocyanate of components (b) and (c), i.e. active hydrogen. In the index of 1.0, there is one functional group reactive with one active hydrogen atom of the components (b) and (c), i.e., isocyanate, per isocyanate group of component (a). At exponents above 1.0, there are more isocyanate groups than OH groups.

Isocyanate prepolymer

For purposes of the present invention, an isocyanate prepolymer is a mixture of (a) isocyanate and (b) isocyanate reactive and has a number average molecular weight in the range from 0.5 kg / mol to 10 kg / mol, preferably from 1 kg / Refers to the reaction product with the compound. The isocyanate prepolymer is the intermediate product of the isocyanate polyation reaction. In a preferred embodiment, the prepolymer has a glass transition temperature Tg of less than -15 DEG C and a melting point of less than 70 DEG C as measured by DSC according to DIN EN ISO 11357-1.

Suitable prepolymers may have an NCO content of preferably 4 to 27 parts by weight, based on the weight of the prepolymer. Suitable prepolymers according to the invention can be used in the form of a single prepolymer or a mixture of prepolymers. In one embodiment of the present invention, a mixture of prepolymers is used.

The most preferred isocyanate prepolymers include diphenylmethane 4,4'-diisocyanate, and / or diphenylmethane 2,2'-diisocyanate, and / or diphenylmethane 2,4'-diisocyanate (MDI) Wherein the molar ratio of the polyester polyol to the diisocyanate is from 1: 1 to 1: 5, preferably from 1: 1 to 1: : 1.2 to 1: 3, more preferably 1: 1.5 to 1: 2.5, such as 1: 2.

In a preferred embodiment, the ratio of 2-methyl-1,3-propanediol to trimethylol propane is such that the polyester polyol has an average functionality > 2, preferably from 2.1 to 3, more preferably from 2.1 to 2.7, 2.2 to 2.5.

In the present invention, the isocyanate prepolymer has an average isocyanate functionality (Fn) of more than 2, preferably 2.1 to 3, more preferably 2.1 to 2.7, more preferably 2.2 to 2.5, most preferably 2.3 to 2.5.

In a preferred embodiment, in order to achieve this isocyanate functionality, the molar ratio of 2-methyl-1,3-propanediol / trimethylol propane is from 53.5 / 1 to 4.5 / 1 when the Mn of the polyester polyol is 1 kg / mol (Fn = 2.1 to 3), 53.5 / 1 to 6.8 / 1 (Fn = 2.1 to 2.7), or 26.3 / 1 to 9.9 / 1 (Fn = 2.2 to 2.5).

Plasticizer

The plasticizer acts as a buried between the chains of the polymer and separates them (increasing the "free volume"), thereby significantly lowering the glass transition temperature of the plastic and softening it. Plasticizers provide improved flexibility and durability to the resulting crosslinked thermoplastic polyurethane.

The plasticizers used in the present invention may be chosen from C _3-15 , preferably C _3-10 , polycarboxylic acids and their linear or branched C _2-30 , esters with aliphatic alcohols, benzoates, epoxidized vegetable oils , Sulfonamides, organic phosphates, glycols and derivatives thereof, and polyethers.

Preferred plasticizers are those selected from the group consisting of sebacic acid, sebacate, adipic acid, adipate, glutaric acid, glutarate, phthalic acid, phthalate (e.g. using C8 alcohol), azelaic acid, azelate, maleic acid, And derivatives thereof, see for example WO 2010/125009, which is hereby incorporated by reference. The plasticizers may be used in combination or individually.

One particular class of preferred plasticizers is phthalate-based plasticizers, such as the phthalate esters of C8 alcohols, which are advantageous because they are resistant to water and oils. Some preferred phthalate plasticizers are bis (2-ethylhexyl) phthalate (DEHP), preferably those used in building materials and medical devices, diisononyl phthalate (DINP), preferably garden hoses, shoes, toys, (DnBP, DBP), butyl benzyl phthalate (BBzP), preferably those used for food conveyor belts, artificial leather, and foams, diisodecyl phthalate (DOP), preferably flooring, carpet, notebook coverings (DIP), preferably those for wire and cable insulation, automotive undercoating, shoes, carpets and full liners; di-n-octyl phthalate , And those used for high performance explosives, diisooctyl phthalate (DIOP), diethyl phthalate (DEP), and diisobutyl phthalate (DIBP), di-n-hexyl phthalate, preferably flooring, tool handles, It will be used for car parts.

Another preferred class of plasticizers are adipates, sebacates and maleates such as bis (2-ethylhexyl) adipate (DEHA), dimethyl adipate (DMAD), monomethyl adipate (MMAD), dioctyl adipate DOA), dibutyl sebacate (DBS), dibutyl maleate (DBM), and diisobutyl maleate (DIBM). Adipate-based plasticizers which are preferably used for low temperature application and high resistance to ultraviolet light are preferred.

Other preferred plasticizers include benzoates, epoxidized vegetable oils, sulfonamides, N-ethyltoluenesulfonamide (o / p ETSA), ortho and para isomers, N- (2- hydroxypropyl) benzenesulfonamide (HP BSA) (TCP), tributyl phosphate (TBP), glycols and derivatives thereof, polyethers such as polyetheretherketone, polyetheretherketone, polyetheretherketone , Such as triethylene glycol dihexanoate (3G6, 3GH), and tetraethylene glycol diheptanoate (4G7).

Another group of preferred plasticizers are biodegradable plasticizers, preferably those that are used as acetylated monoglycerides, preferably as food additives, alkyl citrate, and also preferably as food packaging, pharmaceutical articles, cosmetics, (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), in particular compatible with PVC and vinyl chloride copolymers (ATC), preferably those used in printing inks, trihexyl citrate (THC), trioctyl citrate (THC), trioctyl citrate (THC) Preferably used in a controlled-release medicine, acetyl trihexyl citrate (ATHC), butyryl trihexyl citrate, also referred to as BTHC, tri Hexyl o-butyryl citrate, trimethyl citrate (TMC), alkyl sulfonic acid phenyl ester (ASE).

A further preferred group of plasticizers used in combination with thermoplastic polyurethanes and prepolymers in accordance with the present invention is selected from the group of phthalic acid esters, citric acid esters, adipic acid esters and cyclohexanedicarboxylic acid esters.

The most preferred group of plasticizers are cyclohexane dicarboxylic acid and its esters, more preferred are esters of 1,2-cyclohexane dicarboxylic acid, and alkyl esters wherein each alkyl structure has 3 to 30 carbon atoms Even more preferred, the most preferred plasticizer in combination with thermoplastic polyurethanes and isocyanate prepolymers in accordance with the present invention is 1,2-cyclohexane dicarboxylic acid diisononyl ester (BASF trade name: DINCH®).

In one preferred embodiment, the plasticizer has a boiling point at 1.013 x 10 ⁵ Pa of at least 10 ° C, more preferably 20 ° C, and most preferably at least 50 ° C higher than the melting point of the thermoplastic polyurethane. The boiling point of the plasticizer is measured according to ASTM D1078-11 at vacuum pressure and corrected to the boiling point at 1.013 x 10 &lt; ⁵ &gt; As used herein, the term "melting point" refers to the melting of a heating curve measured at a heating rate of 20 [deg.] C / min in accordance with DIN EN ISO 11357-1 using a commercially available DSC device (e.g., DSC 7 from Perkin- Means the maximum value of the peak. The vaporization temperature of the plasticizer is more than 200 DEG C, more preferably more than 220 DEG C, even more preferably more than 250 DEG C and most preferably 300 DEG C at 1.013 x 10 ⁵ Pa according to ASTM D1078-11 . The water content of the plasticizer is preferably less than 0.1% by weight, more preferably less than 0.05% by weight and most preferably less than 0.02% by weight. The moisture content is determined according to ASTM E1064. The plasticizer has an acid value measured according to ASTM D-1045 of less than 0.1 mg KOH / g.

In a preferred embodiment, the plasticizer is mixed with the starting material of the isocyanate prepolymer such that it is included in the latter.

In one preferred embodiment, the prepolymer composition according to the present invention comprises 1% to 50%, more preferably 2% to 20% and even more preferably 4% to 10% by weight of the plasticizer outlined above, And most preferably about 5 wt%, and a further preferred plasticizer is 1,2-cyclohexanedicarboxylic acid diisononyl ester (BASF trade name: DINCH®).

PMDI

PMDI, which is known as an isocyanate important for polyurethane generation, is a polymethylene polyphenyl polyisocyanate as shown below, and more preferably PMDI is a mixture of compounds having the formula as shown below:

A PMDI suitable for the present invention may be in the form of a homopolymer, a copolymer, or a mixture thereof. Without limitation, a suitable PMDI according to the present invention may have a functionality of from about 2 to 6, preferably from about 2 to 4, more preferably from about 2.5 to 3. [ Examples of PMDI for use in the present invention include, but are not limited to, those commercially available from BASF SE under the trade name Lupranate®, such as Lupranate® M20S and M20R.

In one preferred embodiment, the isocyanate prepolymer composition comprises from 1 wt% to 56 wt%, more preferably from 10 wt% to 50 wt%, even more preferably from 25 wt% to 50 wt% of PMDI.

Additional substance

For the purposes of the present invention, the additional material refers to any material to be added to the reaction system of the thermoplastic polyurethane, the isocyanate prepolymer and the plasticizer, but does not include the thermoplastic polyurethane, the isocyanate prepolymer and the plasticizer. These materials generally include adjuvants and additives commonly used in the art, as indicated above under the subtitle "thermoplastic polyurethane ".

Processing step in the production of cross-linked thermoplastic polyurethane

Crosslinked thermoplastic polyurethanes are prepared by reacting the following components:

Thermoplastic polyurethane; And

An isocyanate prepolymer composition according to the present invention.

In one particular embodiment, the process for preparing a crosslinked thermoplastic polyurethane of the present invention comprises reacting the following components:

Thermoplastic polyurethane;

An isocyanate prepolymer composition according to the present invention; And

Additional substances.

In a preferred embodiment, the crosslinked thermoplastic polyurethane is formed from 1) and 2) below:

One) Diphenylmethane 4,4'-diisocyanate (4,4'-MDI),

1,4-butanediol (as a chain extender), and

It is also possible to use a mixture of at least one polyester polyol and at least one polyether polyol, preferably adipic acid and ethylene glycol, and / or 1,4'-butanediol, and / or 2-methyl- Based polyester polyols; Even more preferably, the polyester polyol comprises 2-methyl-1,3-propanediol and 1,4-butanediol and the polyether polyol comprises polytetrahydrofuran (PTHF), wherein the polyester polyol is a polyol It is used in an amount of more than 40% by weight, preferably more than 60% by weight, more preferably more than 80% by weight, and most preferably more than 90% by weight, based on the total weight of the mixture

Based thermoplastic polyurethane; And

2) Diphenylmethane 4,4'-diisocyanate (4,4'-MDI) and polyols, more preferably polyester polyols, even more preferably adipic acid, 2-methyl-1,3-propanediol and trimethyl An isocyanate prepolymer prepared from a polyester polyol based on an olopropane;

PMDI, for example Lupranate® M20S or M20R, commercially available from BASF SE; And, optionally,

A plasticizer, preferably 1,2-cyclohexanedicarboxylic acid diisononyl ester (BASF trade name: DINCH®)

&Lt; / RTI &gt;

In the present invention, the isocyanate prepolymer composition preferably has an isocyanate functionality of more than 2, preferably in the range of 2.1 to 3, more preferably in the range of 2.1 to 2.7, and most preferably in the range of 2.2 to 2.5.

In another preferred embodiment, the reaction product of the thermoplastic polyurethane and the isocyanate prepolymer composition has a melting point of kofler at 1.013 x 10 &lt; ⁵ &gt; Pa of more than 180 DEG C, more preferably more than 220 DEG C, Gt; 250 C. &lt; / RTI &gt; The Kopler melting point refers to the temperature at which the reaction product changes from solid to liquid after being placed on a hot metal strip of the Kopler bench for one minute.

In one particular embodiment, if a plasticizer is present in the composition, the isocyanate prepolymer is first mixed with the plasticizer, then mixed with PMDI to form a mixture, and then the mixture is mixed with the molten thermoplastic polyurethane, Mix.

In a further particular embodiment, the method is carried out in a molding apparatus; Thus, the reaction between the components and the molding progress simultaneously. In such embodiments, the final product may be formed of a crosslinked thermoplastic polyurethane product such as a film, a fiber, a coating, a damping element, a seal, a bellow, a building or transport flooring, a cable, A trims in an outer cover, a laminate, a profile, a belt, a roller, a hose, a tow cable, a sole, a solar module, a plug connection, an automobile or a wiper blade and is preferably an automobile part, a fiber, a film, a cable, a hose or a shoe, It is a spun elastic fiber.

Additionally, chemical and / or physical blowing agents or gases may be introduced into the thermoplastic polyurethane compositions of the present invention. The foamed product is produced in this manner.

In the case of products of melt-spun elastic fibers, the method may comprise the following steps:

(1) melting thermoplastic polyurethane in an extruder at a temperature of from 180 캜 to 220 캜;

(2) adding an isocyanate prepolymer composition according to the present invention to the molten thermoplastic polyurethane and mixing the resulting mixture to form a melt;

(3) extruding the melt using a spinning nozzle heated at 190 캜 to 230 캜 to obtain a melt-spun elastic fiber.

Optionally, the method further comprises the following steps:

(4) spraying the finish oil onto the fibers, wherein the finish oil may be a mineral oil and / or a silicone oil;

(5) winding the fibers through a roller at a linear velocity of 100 to 1000 m / min;

(6) Storing the fibers at 80 DEG C for at least 15 hours.

In such a process, the isocyanate prepolymer composition according to the present invention is heated and used at a temperature of more than 20 캜 to have a better flowability, and the temperature of the isocyanate prepolymer composition according to the present invention is lowered by an undesired reaction such as an allophanate crosslinking To avoid this, it should be less than 80 ℃. The limiting factor is therefore the high viscosity of the isocyanate prepolymer. Surprisingly, it has been found that by combining PMDI and optionally a plasticizer with an isocyanate prepolymer to form a composition as described above, the viscosity of the isocyanate prepolymer composition can be substantially reduced and the equipment for ultra high pressure applications is not designed, And a reaction product of an isocyanate prepolymer composition with a thermoplastic polyurethane having a higher temperature resistance can be obtained.

In one embodiment, the PMDI and / or plasticizer is added to the mixture of thermoplastic polyurethane, isocyanate prepolymer and / or isocyanate prepolymer and thermoplastic polyurethane.

In one embodiment, the thermoplastic polyurethane and / or isocyanate prepolymer is mixed with PMDI and / or plasticizer.

More preferably PMDI and / or a plasticizer is added to the isocyanate prepolymer.

Preferably, the plasticizer is 1,2-cyclohexanedicarboxylic acid diisononyl ester (BASF trade name: DINCH®) and PMDI has the chemical structure as shown below:

A PMDI suitable for the present invention may be in the form of a homopolymer, a copolymer, or a mixture thereof. Without limitation, a suitable PMDI according to the present invention has a functionality of about 2 to 6, preferably about 2 to 4, more preferably about 2.5 to 3. Examples of PMDI for use in the present invention include, but are not limited to those commercially available from BASF SE under the trade name Lupranate®, such as Lupranate® M20S and M20R.

Preferably, the mixture comprising the prepolymer composition has a viscosity of less than 8 Pa _* s, more preferably less than 6 Pa _* s, as measured by a commercially available rheometer (e. G. HAAKE Rheostress 1) And most preferably less than 5 Pa _* s.

To prepare the reaction product, the thermoplastic polyurethane is preferably preheated to a temperature of from 80 DEG C to 110 DEG C and held at this temperature for a predetermined time, for example 3 hours, to dry the thermoplastic polyurethane. The thermoplastic polyurethane is then placed in an injection molding machine or extruder to melt the thermoplastic polyurethane. The temperature is preferably set at 160 캜 to 280 캜, more preferably at 180 캜 to 250 캜, and still more preferably at 180 캜 to 220 캜. The isocyanate prepolymer is preferably preheated to a temperature of from 40 DEG C to 90 DEG C, more preferably from 50 DEG C to 80 DEG C, and then added to an injection molding machine or extruder and mixed with the molten thermoplastic polyurethane. PMDI and / or plasticizers are recognized as being introduced in any of the ways described above.

The following examples are intended to illustrate the invention without limiting it.

Example 1

Preparation of polyester polyols having an average functionality of 2.2 and a number average molecular weight of 1 kg / mol.

477.5 g (5.31 mol) of 2-methyl-1,3-propanediol and 26.8 g (0.2 mol) of trimethylol propane were reacted at 225 DEG C to 230 DEG C on a mechanical stirrer, thermometer , And a 2-liter three-necked flask equipped with a distillation head. Distillation was continued under reduced pressure (33 kPa) until the distillation rate was greatly reduced and the mixture became clear, until an acid value of less than 0.3 mg KOH / g was detected according to ASTM D-1045.

Examples 2-8 below are for the preparation of isocyanate prepolymers and their compositions.

Example 2 (Comparative Example)

2000 g of a polyester diol having a number average molecular weight of 2 kg / mol (obtained from adipic acid, 2-methyl-1,3-propanediol and 1,4-butanediol) (the latter two having a mass ratio of 1: ) (Commercially available from BASF as Lupraphen® 6610/1) was added to 500 g of diphenylmethane-4,4'-diisocyanate with mechanical stirring and the reaction mixture temperature was controlled between 50 ° C and 65 ° C. After all the polyester diols were added, the reaction mixture was allowed to react at 70 DEG C for an additional 3 hours.

Example 3 (Comparative Example)

12.1 g of trimethylolpropane was mixed with 735.5 g of Lupraphen 6610/1 and then this mixture was added to 252.4 g of diphenylmethane-4,4'-diisocyanate with mechanical stirring and the reaction mixture temperature was maintained at 50 ° C To 65 [deg.] C. After all polyols had been added, the reaction mixture temperature was maintained at 70 캜 for an additional 3 hours.

Example 4 (Comparative Example)

600 g of polyol prepared according to Example 1 were added to 346 g of diphenylmethane-4,4'-diisocyanate with mechanical stirring and the temperature of the reaction mixture was controlled between 50 ° C and 65 ° C. After all polyols had been added, the reaction mixture temperature was maintained at 70 캜 for an additional 3 hours.

Example 5 (Inventive)

519 g of diphenylmethane-4,4'-diisocyanate and 157.7 g of 1,2-cyclohexanedicarboxylic acid diisononyl ester were mixed and to this mixture, 905.9 g of polyol prepared according to Example 1 Was added under mechanical stirring. The temperature of the reaction mixture was controlled at 50 캜 to 65 캜. After all the polyols had been added, the reaction mixture temperature was maintained at 70 DEG C for an additional 3 hours.

Example 6 (Inventive)

500 g of the isocyanate prepolymer composition prepared according to Example 5 were mixed with 167 g of PMDI (BASF, Lupranate 占 M20S) at 60 占 폚.

Example 7 (Inventive)

500 g of the isocyanate prepolymer composition prepared according to Example 5 was mixed with 250 g of polymethylene polyphenyl polyisocyanate (BASF, Lupranate M20S) at 60 占 폚.

Example 8 (Inventive)

500 g of the isocyanate prepolymer composition prepared according to Example 5 were mixed with 500 g of polymethylene polyphenyl polyisocyanate (BASF Lupranate (R) M20S) having a functionality of about 2.7 at 60 캜.

Viscosity of isocyanate prepolymer / prepolymer composition Example 2 (C) 3 (C) 4 (C) 5 6 7 8 Viscosity
(Pa _* s at 75 [deg.] C) 5.0 8.5 9.0 5.5 2.0 1.3 0.8

From Table 1 it can be seen that the plasticizer reduces the viscosity of the isocyanate prepolymer composition and the viscosity is further reduced by additional PMDI (BASF SE, Lupranate® M20S).

Examples 9-15

In these examples, the melt-spun elastomeric fibers were prepared by the following process:

(1) thermoplastic polyurethanes such as BASF TPU such as BASF Elastollan® 2280A10 (4,4'-MDI, 1,4-butanediol, polytetramethylene ether glycol with a molecular weight of 1000 g / mol and Lupraphen® 6610 / 1) in a single screw extruder at a temperature of 190 占 폚 or as directed;

(2) adding the prepolymer or prepolymer composition obtained in Example 2-8 to the molten TPU of step (1) and mixing them to form a melt;

(3) extruding the melt through a spinneret heated at 200 DEG C or as directed to obtain melt-spun elastomeric fibers;

(4) spraying the finish oil onto the fibers, wherein the finish oil is a silicone oil;

(5) winding the fiber through a roller at a linear velocity of 500 m / min;

(6) Storing the fibers at 80 DEG C for 15 hours for better compatibility.

Example 9 (Comparative Example)

880 g of Elastollan® 2280A10, 120 g of the isocyanate prepolymer of Example 2, at a spinning temperature of 200 ° C.

Example 10 (Inventive)

880 g of Elastollan® 2280A10, 120 g of the isocyanate prepolymer of Example 3, at a spinning temperature of 210 ° C.

Example 11 (Inventive)

880 g of Elastollan® 2280A10, 120 g of the isocyanate prepolymer of Example 4, at a spinning temperature of 209 ° C.

Example 12 (Inventive)

870 g of Elastollan® 2280A10, 130 g of the isocyanate prepolymer of Example 5, at a spin valve temperature of 205 ° C.

Example 13 (Inventive)

940 g of Elastollan® 2280A10, 60 g of the isocyanate prepolymer composition of Example 6, at a spinning temperature of 198 ° C.

Example 14 (Inventive)

940 g of Elastollan® 2280A10, 60 g of the isocyanate prepolymer composition of Example 7, at a spinning temperature of 201 ° C.

Example 15 (Inventive)

940 g of Elastollan® 2280A10, 60 g of the isocyanate prepolymer composition of Example 8, at a spin valve temperature of 204 ° C.

Example 16 (Comparative Example)

One commercially available one 20D melt-spun elastomeric fiber manufactured by Jiangsu Nanhuanghai Industry commerce Co.,

Processing conditions and properties of fiber products Example 9 (C) -2 ^c 10-3 11-4 12-5 13-6 14-7 15-8 16 (C) Spray temperature (℃) ^a 200 210 209 205 204 201 198 N.A. Copper melting point (° C) ^b 198 220 220 215 230 240 250 200

^{a The} spinneret temperature may vary due to the design of the melt spinning equipment.

^{The b} Copper melting point refers to the temperature at which the fibers change from solid to liquid after the fibers are placed on a hot metal strip of the CopperBench for one minute.

^c 9-2 refers to Example 9 using the isocyanate prepolymer of Example 2.

From Table 2 it can be seen that the fibers with the isocyanate prepolymer composition according to the invention (Examples 10 to 15) exhibit improved high temperature resistance over fibers made from isocyanate prepolymer of TPU and functionality = 2. The disclosed fibers also exhibit improved high temperature resistance over commercially available melt-spun elastomeric fibers.

Claims (17)

Isocyanate prepolymer;
Polymethylene polyphenyl polyisocyanate (PMDI) having the chemical structure shown below

; And, optionally,
An isocyanate prepolymer composition comprising a plasticizer, wherein said prepolymer has an average isocyanate functionality of from 2.1 to 3. The isocyanate prepolymer composition of claim 1, wherein the isocyanate prepolymer is a reaction product of (a) an isocyanate and (b) a compound reactive with isocyanate and having a number average molecular weight in the range of 0.5 kg / mol to 10 kg / mol. 3. The composition of claim 1 or 2, wherein the isocyanate prepolymer is selected from the group consisting of diphenylmethane 4,4'-diisocyanate, and / or diphenylmethane 2,2'-diisocyanate, and / or diphenylmethane 2,4'-di (MDI) with a polyester polyol based on adipic acid, 2-methyl-1,3-propanediol and / or trimethylol propane, the molar ratio of said polyester polyol to said diisocyanate being 1: 1 to 1: 3, preferably 1: 1.5 to 1: 2.5, more preferably 1: 2. 4. The process of any one of claims 1 to 3 wherein the isocyanate prepolymer is prepared by reacting diphenylmethane 4,4'-diisocyanate with adipic acid, 2-methyl-1,3-propanediol and trimethylolpropane-based poly Wherein the ratio of 2-methyl-1,3-propanediol and trimethylol propane is such that the average functionality of the polyester polyol is > 2, preferably 2.1 to 3, more preferably 2.1 to 2.7, Most preferably 2.2 to 2.5. &Lt; Desc / Clms Page number 13 &gt; 5. The isocyanate prepolymer composition according to any one of claims 1 to 4, wherein the PMDI has an average functionality of 2 to 6, preferably 2 to 4, more preferably 2.5 to 3. 6. The isocyanate prepolymer composition according to any one of claims 1 to 5, wherein PMDI is selected from Lupranate 占 M20S, M20R and mixtures thereof. 7. The isocyanate prepolymer composition according to any one of claims 1 to 6, wherein the prepolymer has an average isocyanate functionality of 2.1 to 2.7, most preferably 2.2 to 2.5. A process for preparing an isocyanate prepolymer composition according to any one of claims 1 to 7, comprising mixing an isocyanate prepolymer, PMDI and, if desired, a plasticizer. 9. The method of claim 8, wherein the PMDI and / or plasticizer is mixed with the starting material of the isocyanate prepolymer, or if the plasticizer is present in the prepolymer composition, the isocyanate prepolymer is first mixed with the plasticizer and then mixed with the PMDI. A crosslinked thermoplastic polyurethane composition essentially comprising the reaction product of the following components:
Thermoplastic polyurethane;
An isocyanate prepolymer composition according to any one of claims 1 to 7; And, optionally,
Additional substances. 11. The crosslinked thermoplastic polyurethane composition of claim 10, wherein the crosslinked thermoplastic polyurethane composition is in the form of fibers. 11. A process for the preparation of the crosslinked thermoplastic polyurethane composition according to claim 10 or claim 11 comprising reacting the following components:
Thermoplastic polyurethane;
An isocyanate prepolymer composition according to any one of claims 1 to 7; And, optionally,
Additional substances. 13. The method of claim 12, wherein the PMDI and / or plasticizer is added to a mixture of a thermoplastic polyurethane, an isocyanate prepolymer and / or an isocyanate prepolymer and a thermoplastic polyurethane. 14. A process according to claim 12 or claim 13, wherein the PMDI and / or plasticizer is mixed with the starting material of the isocyanate prepolymer, or if the plasticizer is present in the composition, the isocyanate prepolymer is first mixed with the plasticizer, Way. 11. A process for the preparation of the crosslinked thermoplastic polyurethane composition according to claim 10 or claim 11 comprising the following steps:
(1) melting the thermoplastic polyurethane at a temperature of 180 ° C to 220 ° C in an extruder;
(2) adding an isocyanate prepolymer composition according to any one of claims 1 to 7 to the molten thermoplastic polyurethane and mixing the resulting mixture to form a melt; And
(3) Extruding the melt through a heated spinneret at 190 ° C to 230 ° C to obtain melt-spun elastic fibers. 16. The method of claim 15, further comprising the following steps:
(4) spraying a finish oil onto the fibers, wherein the finish oil may preferably be a mineral oil and / or a silicone oil;
(5) winding the fibers through a roller at a linear velocity of 100 to 1000 m / min; And
(6) Storing the fibers at 80 DEG C for at least 15 hours. Use of PMDI and / or a plasticizer in making an isocyanate prepolymer composition or a crosslinked thermoplastic polyurethane.