CN108192509B

CN108192509B - Composite fireproof glass and preparation method thereof

Info

Publication number: CN108192509B
Application number: CN201711119456.XA
Authority: CN
Inventors: 侯少华
Original assignee: Hebei Minghua Jinying Glass Technology Co ltd
Current assignee: Hebei Minghua Jinying Glass Technology Co ltd
Priority date: 2017-11-14
Filing date: 2017-11-14
Publication date: 2020-12-29
Anticipated expiration: 2037-11-14
Also published as: CN108192509A

Abstract

The invention relates to the field of fireproof glass, in particular to composite fireproof glass and a preparation method thereof. The polyurethane film for the composite fireproof glass at least comprises, by weight, 50-65 parts of polyol, 7-12 parts of isocyanate, 0.1-0.2 part of catalyst, 2-14 parts of chain extender and 15-26 parts of modifier.

Description

Composite fireproof glass and preparation method thereof

Technical Field

The invention relates to the field of fireproof glass, in particular to composite fireproof glass and a preparation method thereof.

Background

Fire-resistant glass is a special type of glass that maintains its integrity, thermal insulation and radiant heat intensity requirements under specified fire test conditions. It first appeared in europe in the early 70's of the 20 th century. It belongs to one of the members of the family of architectural safety glass, also called special glass. The fireproof glass has the characteristics of transparency, capability of blocking and controlling heat radiation and smoke, capability of preventing flame and fire from spreading and the like. In addition, the fireproof glass also has certain impact strength and has a protective effect under the condition of flame at about 1000 ℃.

Modern floor building window area is bigger and bigger, and pleasing to the eye, functional glass component receives the home and abroad designer's favor, and various safety glass and special glass gradually become the building glass trade of beauty. As architectural glass, there have been developed various functions such as controlling light, adjusting room temperature, preventing noise, and improving environment, which have been used as a mere lighting and decorative material in the past. Fire-proof glass, as one of the building safety glass, has not only some properties of ordinary glass, but also properties of controlling fire spread or isolating smoke. The fire disaster rescue device creates important conditions for rescue of personnel, property and buildings when a fire disaster occurs, and reduces loss to the maximum extent. In recent years, people begin to deeply discuss and pay attention to the quality of fire-proof materials after the frequent fire of large buildings, especially after the fire of people who enter and visit buildings in the north of new courts.

The fireproof glass is mainly used in the fields of public buildings such as various exhibition halls, television broadcasting buildings, banks, airports, libraries, shopping malls, theaters, finance, trade buildings, hotels, staircases of restaurants, lifting shafts, corridors, platforms and the like, and is used for fireproof doors, fireproof walls, fireproof partitions, fireproof doors and windows and the like. The fireproof material is applied to national defense and scientific research facilities, such as major biological and chemical factories and laboratories, and fireproof doors, windows and partitions in inflammable and explosive buildings. In addition, the fireproof glass used in the matching field of space flight facilities such as rockets, satellites and the like is more than the same. In the aspect of transportation, special fireproof glass is the most important of high-speed vehicles and ships, especially luxury passenger ships and military ships. At present, the major international producing countries are british, france, germany, japan, belgium, and the united states, russia, china, and the like.

The fire-proof glass is classified according to structure and can be divided into composite fire-proof glass and single-layer fire-proof glass. The composite fireproof glass is special glass which is formed by compounding two or more layers of glass or a layer of glass and an organic material and meets the requirement of corresponding fire resistance grade. The production technology of the composite fireproof glass with better fireproof performance is mature at present and is widely used in buildings. However, fire-resistant glass has high requirements for optical properties, mechanical properties, weight, safety and the like, in addition to fire resistance and fire resistance. Therefore, it is necessary to improve the fire resistance and fire resistance of the fire-resistant glass and to improve the safety of the fire-resistant glass so that the fire-resistant glass has some characteristics of the protective glass. Specifically, the bonding strength of the glass adhesive to inorganic glass is improved to prevent the occurrence of degumming and the like of the fireproof glass during use. Meanwhile, the proper film is adopted to absorb the energy generated when the fireproof glass is impacted as much as possible, and the characteristics of improving the impact resistance and the like of the fireproof glass are very necessary.

Disclosure of Invention

In order to solve the technical problems, the first aspect of the invention provides a polyurethane film for composite fireproof glass, and the polyurethane film comprises, by weight, at least 50-65 parts of polyol, 7-12 parts of isocyanate, 0.1-0.2 part of catalyst, 2-14 parts of chain extender and 15-26 parts of modifier.

As a preferable technical scheme, the chain extender contains epoxy groups and hydroxyl groups in a molecular chain.

As a preferred technical solution of the present invention, the chain extender is selected from: 3, 4-butylene oxide-1, 2-diol, 2-bis [ (oxiranylmethoxy) methyl ] propane-1, 3-diol, 1, 19-bis (oxiranylmethoxy) -8, 16-bis (oxiranylmethoxy) -2,6,10,14, 18-pentaoxanonadecane-4, 12-diol, 2- [ (2, 3-epoxypropoxy) methane

One or more of the group ] -2- (hydroxymethyl) propane-1, 3-diol, and (2, 3-epoxypropyl) ethylbis (2-hydroxyethyl) ammonium chloride.

In a preferred embodiment of the present invention, the chain extender further contains an ether bond in a molecular chain.

As a preferable technical scheme of the invention, the molecular chain of the modifier contains organosiloxane groups, hydroxyl groups and/or amino groups.

In a preferred embodiment of the present invention, the catalyst is one or more selected from the group consisting of an organotin-based catalyst, a boron trifluoride-based catalyst, and an amine-based catalyst.

In a preferred embodiment of the present invention, the modifier is selected from one or more of 3-aminopropyltrimethoxysilane, (4-amino-3, 3-dimethylbutyl) methyldimethoxysilane, 4-amino-3, 3-dimethylbutyltrimethoxysilane, hydroxyl-terminated polymethyl 3,3, 3-trifluoropropylsiloxane, hydroxyl-terminated polydimethylsiloxane, 3- (ethylamino) -2-methylpropyl-terminated polydimethylsiloxane, aminopropyl-di-terminated polydimethylsiloxane, and hydroxyl-terminated poly (3-aminopropylvinyl) silsesquioxane.

The second aspect of the invention provides a preparation method of a polyurethane film for composite fireproof glass, which at least comprises the following steps:

the first step is as follows: adding polyol and a catalyst into a reaction kettle, adding isocyanate under the condition of introducing nitrogen, and enabling the molar ratio of hydroxyl to isocyanate in a system to be 1: (1.6-2), and reacting for 2-4 hours at 35 ℃ under stirring to obtain a polyurethane prepolymer;

the second step is that: dissolving the polyurethane prepolymer obtained in the first step in a solvent, and adding a chain extender to ensure that the molar ratio of the amount of the chain extender to the polyol used in the first step is (0.6-1): 1, stirring and mixing at 50-60 ℃, and reacting for 2-4 hours;

the third step: and dissolving a modifier in DMSO, adding boron trifluoride diethyl etherate which is 1-2 wt% of the amount of the chain extender in the second step, stirring and mixing, adding the mixture into the reaction system in the second step, heating the temperature of the system to 90-120 ℃, reacting for 2-4 hours under stirring, concentrating and removing the solvent to obtain the polyurethane sheet for the composite fireproof glass.

A third aspect of the present invention provides a composite fire-resistant glass having a multilayer structure; the multilayer structure comprises an inorganic glass layer, an organic transparent material layer and an intermediate cementing layer; the inorganic glass layer is made of inorganic float glass; the material of the organic transparent material layer is polycarbonate; the raw material of the middle cementing layer is the polyurethane sheet for the composite fireproof glass provided by the first aspect of the invention.

The fourth aspect of the invention provides a preparation method of the composite fireproof glass, which at least comprises the following steps:

(1) cleaning the surfaces of the inorganic glass layer and the organic transparent material, and drying;

(2) stacking the organic transparent material, the intermediate cementing layer and the inorganic glass layer in sequence under the conditions of constant temperature and constant humidity, and stacking the intermediate cementing layer between the organic transparent material and the inorganic glass layer;

(3) placing the stacked laminated glass in a vacuum bag or a vacuum ring, vacuumizing for 15-30 min, and removing gas between layers;

(4) and (4) placing the laminated glass obtained in the step (3) in an autoclave, and carrying out hot pressing for 15-30 min at 110-125 ℃ and 1-1.2 MPa to obtain the composite fireproof glass.

The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.

Has the advantages that: when the ordinary glass meets a big fire, the glass is easy to explode when absorbing heat, and under the condition of fire, the glass can not play a role in fire prevention and separation because the fire can rapidly spread to cause fire disaster and cause fire hazard, so that the application of the glass is limited. The inventor unexpectedly discovers that the composite fireproof glass provided by the invention has very good fireproof performance, can meet the fireproof integrity, controls the spread of fire, has the fireproof time of more than 90 minutes under the standard fireproof test condition, has the fireproof grade I, and can be used as ideal fireproof glass in the fields of public buildings such as high-grade hotels, movie theaters, exhibition halls, airports, gymnasiums, hospitals, libraries, shopping malls and the like, and fireproof doors, fireproof windows, fireproof partitions and the like of public buildings. In addition, the contact angle of the polyurethane film solution for the composite fireproof glass provided by the invention on the inorganic glass layer is as low as 63 degrees, which is nearly half of that of the polyurethane film solution without modification. In addition, the composite fireproof glass provided by the invention has good impact resistance, and has great substantial progress on the performances of inorganic glass such as bonding strength, shear strength and the like compared with the common composite glass, and the contact area and acting force between the polyurethane film and the inorganic glass in the hot press molding process of the composite fireproof glass are greatly improved, so that the obtained composite fireproof glass has good wearability.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The term "and/or" as used herein means both or either of the following, for example: "include C, A and/or B" is intended to include: "including C, A, B", "including C, A" and "including C, B".

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".

In the present invention, the polyol is not particularly limited, and there may be exemplified: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, alkanediol (7 to 22), diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, alkane1, 2-diol (C17 to 20), 1, 3-or 1, 4-cyclohexanedimethanol, and mixtures thereof, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, 8-diol, and dihydric alcohols such as bisphenol A, for example, triols such as glycerol and trimethylolpropane, for example, tetramethylolmethane (pentaerythritol), Tetrahydric alcohols such as diglycerin, for example, pentahydric alcohols such as xylitol, for example, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, for example, heptahydric alcohols such as mannitol, and octahydric alcohols such as sucrose, for example.

The polyol may also be a polymer polyol, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols.

Examples of the polyether polyol include polypropylene glycol and polytetramethylene ether glycol.

Examples of the polyester polyol include polycondensates obtained by reacting the low-molecular-weight polyol (preferably, diol) with a polybasic acid under known conditions.

Examples of the polycarbonate polyol include a ring-opened polymer of ethylene carbonate using the above-mentioned low-molecular-weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing a diol such as 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol or 1, 6-hexanediol with a ring-opened polymer.

The polyurethane polyol can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, a polyester polyether polyurethane polyol or the like by reacting the polyester polyol, the polyether polyol and/or the polycarbonate polyol obtained as described above with the polyisocyanate (containing 1, 4-bis (isocyanatomethyl) cyclohexane) at a ratio of the equivalent ratio of hydroxyl groups to isocyanate groups (OH/NCO) of more than 1.

Examples of the epoxy polyol include epoxy polyols obtained by reacting the low-molecular-weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β -methyl epichlorohydrin.

Examples of the vegetable oil polyol include vegetable oils containing hydroxyl groups such as castor oil and coconut oil. Examples thereof include castor oil polyol, and ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

Examples of the polyolefin polyol include polyvinyl alcohol, polyethylene glycol, polybutadiene polyol, and partially saponified ethylene-vinyl acetate copolymer.

Examples of the acrylic polyol include copolymers obtained by copolymerizing an acrylate having a hydroxyl group and a copolymerizable vinyl monomer copolymerizable with the acrylate having a hydroxyl group.

In a preferred embodiment, the polyol is selected from the group consisting of: any one or mixture of more of polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol and acrylic polyol.

In a preferred embodiment, the polyol is polytetramethylene ether glycol.

In the present invention, the isocyanate compound is not particularly limited, and there may be mentioned: aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, polyisocyanates, and the like.

Examples of the aliphatic diisocyanate include propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, 2, 4, 4-or 2,2, 4-trimethyl 1, 6-hexamethylene diisocyanate, and methyl 2, 6-diisocyanatohexanoate.

Examples of the alicyclic diisocyanate include 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane isocyanate (also known as isophorone diisocyanate), 4' -methylenebis (cyclohexyl isocyanate), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatoethyl) cyclohexane, 1, 4-bis (isocyanatoethyl) cyclohexane, 2, 5-or 2, 6-bis (isocyanatomethyl) Norbornane (NBDI), mixtures thereof and the like.

Examples of the aromatic diisocyanate include: 2, 4-tolylene diisocyanate and2, 6-tolylene diisocyanate, and isomer mixtures of the aforementioned tolylene diisocyanates, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and2, 2 ' -diphenylmethane diisocyanate, and arbitrary isomer mixtures of the aforementioned diphenylmethane diisocyanates, tolylene diisocyanates, p-phenylene diisocyanates, naphthalene diisocyanates, and the like.

Examples of the aliphatic triisocyanate include 1,3, 6-triisocyanate methylhexane and the like.

Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanates and polyisocyanates derived from the diisocyanate compounds. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate polyisocyanates, biuret polyisocyanates, urethane polyisocyanates, allophanate polyisocyanates, and carbodiimide polyisocyanates.

In a preferred embodiment, the isocyanate is hexamethylene diisocyanate.

In a preferred embodiment, the catalyst is selected from one or more of an organic butyltin-based catalyst, a boron trifluoride-based catalyst, and an amine-based catalyst.

In the present invention, the catalyst is an organotin-based catalyst and a boron trifluoride-based catalyst, including but not limited to dibutyltin dilaurate and boron trifluoride etherate.

Dibutyltin dilaurate is an organic tin additive, and can be dissolved in organic solvents such as benzene, toluene, carbon tetrachloride, ethyl acetate, chloroform, acetone, petroleum ether and the like and industrial plasticizers. The multipurpose high boiling point organotin catalyst dibutyltin dilaurate in the market is usually liquefied specially, is light yellow or colorless oily liquid at normal temperature, is white crystal at low temperature, can be used for polyvinyl chloride plastic additives, and has excellent lubricating property, transparency and weather resistance. The sulfide pollution resistance is better. It can be used as stabilizer in soft transparent product, high-effective lubricant in hard transparent product, catalyst for cross-linking reaction of acrylate rubber and carboxyl rubber, synthesis of polyurethane foam plastics and synthesis of polyester, and catalyst for room-temp. vulcanized silicone rubber. The dibutyltin dilaurate is used as a catalyst to catalyze the reaction between isocyanate groups and hydroxyl, amino and other groups. Boron trifluoride ethyl ether catalyzes epoxy group to perform ring-opening reaction with hydroxyl or amino, and the modifier is grafted in a polyurethane molecular chain.

The chain extender in the invention is dihydric alcohol containing epoxy groups, and hydroxyl reacts with residual isocyanate groups in the polyurethane prepolymer to expand molecular chains of polyurethane and increase molecular weight of the polyurethane. Meanwhile, the dihydric alcohol also contains an epoxy group, so that a polyurethane molecular chain obtained by final reaction has a branched chain containing the epoxy group, and the epoxy group is relatively active, so that the surface energy of the polymer is improved, the acting force between the polymer and inorganic glass and the like can be improved, and the bonding strength is improved.

In a preferred embodiment, the chain extender contains epoxy groups and hydroxyl groups in the molecular chain.

In addition, the epoxy group in the molecular chain can react with functional groups such as amino groups, hydroxyl groups (can react with the hydroxyl groups under the action of an amine catalyst) and the like, so that some functional groups can be introduced into the polyurethane molecular chain to further perform functional modification on polyurethane molecules.

And the chain extender simultaneously contains ether bonds in a molecular chain, and because the internal rotation barrier of the ether bonds is small, the dynamic flexibility is good, the flexibility of the polyurethane molecular chain obtained by chain extension of the chain extender is higher, and under the action of thermal excitation or external force, the molecular chain can be more easily converted from an internal rotation heterogeneous sequence to a more favorable internal rotation heterogeneous sequence under the action of external force, so that the flexibility and the impact resistance of the polymer in a macroscopic state are improved.

In a preferred embodiment, the chain extender is selected from the group consisting of: 3, 4-butylene oxide-1, 2-diol, 2-bis [ (oxiranylmethoxy) methyl ] propane-1, 3-diol, 1, 19-bis (oxiranylmethoxy) -8, 16-bis (oxiranylmethoxy) -2,6,10,14, 18-pentaoxanonadecane-4, 12-diol, 2- [ (2, 3-epoxypropoxy) methyl ] -2- (hydroxymethyl) propane-1, 3-diol, or (2, 3-epoxypropyl) ethylbis (2-hydroxyethyl) ammonium chloride.

In a preferred embodiment, the chain extender further contains ether bonds in the molecular chain.

The modifier in the invention is a substance containing groups of organosiloxane and hydroxyl in a molecular chain. The silicon content in the common float glass exceeds 70 percent, so that after functional groups containing organic silicon are introduced into the polyurethane film, on one hand, the surface energy of polyurethane can be improved, the surface tension is weakened, and the wettability and acting force between the polyurethane film and the inorganic glass and organic transparent material layer are improved. In the hot pressing process, organic silicon groups in the polyurethane film can be well infiltrated on the surface of the inorganic glass due to low surface tension, even the organic silicon groups have the characteristics of surface energy, cohesive energy density and the like which are not much different from those of the inorganic glass, and the organic silicon groups can be organically diffused into the surface of the inorganic glass, so that the polyurethane film and the inorganic glass layer are better bonded together. On the other hand, the introduction of the organic silicon functional group enables the preparation method of the improved fireproof glass to hydrolyze the organic silicon group and bond with the silicon component in the inorganic glass through a chemical bond, so that the adhesive force and the impact strength between the middle cementing layer and the rest layers in the fireproof glass can be improved more possibly.

And moreover, the polyurethane film contains a siloxane chain segment structure, the structure can improve the oxygen index of the polyurethane film, the carbon formation amount of a system can be increased after the system is combusted, a pyrolysis carbon layer is formed on the surface of the material, and the oxidation resistance of the pyrolysis carbon layer is improved, so that the heat release amount of the material is effectively reduced, the fireproof glass is prevented from being further combusted, and the fireproof performance of the fireproof glass is improved.

In a preferred embodiment, the modifier contains organosiloxane groups, hydroxyl groups and/or amino groups in the molecular chain.

In addition, the modifier contains a functional group of organosilicon and fluorine atoms, so that fluorine atoms with low surface tension are introduced into the molecular chain of the polyurethane film, the contact area of the whole polyurethane molecular chain with the rest layers is increased due to low surface tension in the hot press molding process of the composite fireproof glass, the bonding strength is improved, and the wearability of the composite fireproof glass is further improved.

In a preferred embodiment, as a preferred embodiment of the present invention, the molecular chain of the modifier further contains fluorine atoms.

the third step: and (3) dissolving a modifier in DMSO (dimethyl sulfoxide), adding boron trifluoride ethyl ether in an amount which is 1-2 wt% of the amount of the chain extender in the second step, stirring and mixing, adding the mixture into the reaction system in the second step, heating the temperature of the system to 90-120 ℃, reacting for 2-4 hours under stirring, concentrating and removing the solvent to obtain the polyurethane sheet for the composite fireproof glass.

In the present invention, an isocyanate group-terminated polyurethane prepolymer is obtained by reacting a polyol with an excess of isocyanate, and the molecular weight of polyurethane is increased with an epoxy group-containing chain extender to obtain an epoxy group-containing polyurethane polymer. Then, hydroxyl or amino in the modifier reacts with epoxy groups in polyurethane by utilizing the catalytic action of boron trifluoride diethyl etherate, and the modifier is grafted into a polyurethane molecular chain. Moreover, because the modifier can be a polymer with a relatively large molecular weight, the obtained polyurethane polymer contains branched chains with a certain length, so that the conformation of the polymer is increased, the flexibility is improved, and the impact resistance is improved. In addition, the functional groups such as organosilicon, fluorine and the like in the modifier further improve the bonding performance of the whole polyurethane film for the composite fireproof glass to inorganic glass, organic transparent material layers and the like.

Moreover, the organic silicon functional groups introduced into the polyurethane film for the composite fireproof glass are bonded on the polyurethane molecular chain through chemical bonds, and different from common processing modes such as blending and the like, the organic silicon functional groups have different effects on the improvement of the surface energy of the whole polyurethane molecular chain, the reduction of the contact angle of the polyurethane molecular chain on inorganic glass and the like. Because physical blending generally can not reach molecular level blending, and the action between the organosilicon group and the polyurethane molecule in the blending system is much weaker than the action force of the organosilicon group on chemical bond, the brought effect is general.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the specifications, sources and the like of the same raw materials used in the examples are the same, and the raw materials used are all commercially available and purchased from national chemical reagents unless otherwise specified.

Examples

Example 1

Embodiment 1 provides a polyurethane film for composite fireproof glass, and the raw materials for preparing the polyurethane film comprise, by weight, 50 parts of polyol, 7.4 parts of isocyanate, 0.1 part of catalyst, 4.8 parts of chain extender and 15 parts of modifier.

The polyalcohol is polytetramethylene ether glycol and is purchased from national medicine chemical reagents; the isocyanate is hexamethylene diisocyanate and is purchased from national medicine chemical reagents; the catalyst is dibutyltin dilaurate and is purchased from a national medicine chemical reagent; the chain extender is 2, 2-bis [ (oxiranylmethoxy) methyl ] propane-1, 3-diol (CAS number: 40762-73-0, available from Chemos GmbH company); the modifier was 3-aminopropyltrimethoxysilane (CAS number: 13822-56-5, available from Shanghai Michelin Biotech, Inc.).

The preparation method of the polyurethane film for the composite fireproof glass comprises the following steps:

the first step is as follows: adding polyol and a catalyst into a reaction kettle, adding isocyanate under the condition of introducing nitrogen, and reacting for 2 hours under stirring at 35 ℃ to obtain a polyurethane prepolymer;

the second step is that: dissolving the polyurethane prepolymer obtained in the first step in DMSO, adding a chain extender, stirring and mixing at 50 ℃, and reacting for 2 hours;

the third step: and (3) dissolving a modifier in DMSO, adding boron trifluoride diethyl etherate which is 1 wt% of the amount of the chain extender in the second step, stirring and mixing, adding the mixture into the reaction system in the second step, heating the temperature of the system to 90 ℃, reacting for 2 hours under stirring, concentrating and removing the solvent to obtain the polyurethane film for the composite fireproof glass.

The preparation method of the composite fireproof glass comprises the following steps:

(1) cleaning the surfaces of the inorganic glass layer and the organic transparent material layer, and drying;

(2) stacking an organic transparent material layer, an intermediate cementing layer and an inorganic glass layer in sequence under the conditions of constant temperature and constant humidity, and stacking the intermediate cementing layer between the organic transparent material layer and the inorganic glass layer;

(3) placing the stacked laminated glass in a vacuum bag or a vacuum ring, vacuumizing for 15min, and removing gas between layers;

(4) and (4) placing the laminated glass obtained in the step (3) in a high-pressure kettle, and carrying out hot pressing at 110 ℃ and 1MPa for 15min to obtain the composite fireproof glass.

The inorganic glass layer is common float glass and is purchased from Shanghai Yao leather glass Co Ltd; the organic transparent material layer was a polycarbonate layer, available from Sauter basic industries, Inc.

Example 2

Embodiment 2 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 65, isocyanate 12, catalyst 0.2, chain extender 7.8, and modifier 25.

The polyalcohol is polytetramethylene ether glycol and is purchased from national medicine chemical reagents; the isocyanate is hexamethylene diisocyanate and is purchased from national medicine chemical reagents; the catalyst is dibutyltin dilaurate and is purchased from a national medicine chemical reagent; the chain extender is 2, 2-di [ (ethylene oxide methoxyl) methyl ] propane-1, 3-diol; the modifier is 3-aminopropyl trimethoxy silane.

the first step is as follows: adding polyol and a catalyst into a reaction kettle, adding isocyanate under the condition of introducing nitrogen, and reacting for 4 hours under stirring at 35 ℃ to obtain a polyurethane prepolymer;

the second step is that: dissolving the polyurethane prepolymer obtained in the first step in DMSO, adding a chain extender, stirring and mixing at 60 ℃, and reacting for 4 hours;

the third step: and (3) dissolving a modifier in DMSO, adding boron trifluoride diethyl etherate which is 2 wt% of the amount of the chain extender in the second step, stirring and mixing, adding the mixture into the reaction system in the second step, heating the temperature of the system to 120 ℃, reacting for 4 hours under stirring, concentrating and removing the solvent to obtain the polyurethane film for the composite fireproof glass.

(3) placing the stacked laminated glass in a vacuum bag or a vacuum ring, vacuumizing for 30min, and removing gas between layers;

(4) and (4) placing the laminated glass obtained in the step (3) in a high-pressure kettle, and carrying out hot pressing at 125 ℃ and 1.2MPa for 30min to obtain the composite fireproof glass.

Example 3

Embodiment 3 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 6.4, and modifier 20.

the second step is that: dissolving the polyurethane prepolymer obtained in the first step in DMSO, adding a chain extender, stirring and mixing at 50 ℃, and reacting for 4 hours;

the third step: and (3) dissolving a modifier in DMSO, adding boron trifluoride diethyl etherate which is 1.5 wt% of the amount of the chain extender in the second step, stirring and mixing, adding the mixture into the reaction system in the second step, heating the system to 120 ℃, reacting for 4 hours under stirring, concentrating and removing the solvent to obtain the polyurethane sheet for the composite fireproof glass.

(3) placing the stacked laminated glass in a vacuum bag or a vacuum ring, vacuumizing for 20min, and removing gas between layers;

(4) and (4) placing the laminated glass obtained in the step (3) in a high-pressure kettle, and carrying out hot pressing at 120 ℃ and 1.2MPa for 20min to obtain the composite fireproof glass.

Example 4

Embodiment 4 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 2.7, and modifier 20.

The raw material for preparing the polyurethane film for the composite fire-proof glass is different from that of the example 3 in that the chain extender adopts 3, 4-butylene oxide-1, 2-diol (CAS number: 17177-50-3, available from SYNCHEM-OHG) with the same molar amount.

The preparation method of the polyurethane film for the composite fireproof glass is the same as that of the example 3.

The composite fire-resistant glass was prepared in the same manner as in example 3.

Example 5

Embodiment 5 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 7, and modifier 20.

The raw materials for preparing the polyurethane film for the composite fire-proof glass are different from those in example 3 in that the chain extender adopts the same molar amount of 2- [ (2, 3-epoxypropoxy) methyl ] -2- (hydroxymethyl) propane-1, 3-diol (CAS number: 55206-69-4, available from Chemos GmbH company).

Example 6

Embodiment 6 provides a polyurethane film for composite fire-resistant glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 5.8, and modifier 20.

The preparation raw material of the polyurethane film for the composite fireproof glass is different from that of the polyurethane film for the example 3 in that the chain extender adopts the same molar amount of (2, 3-epoxypropyl) ethyl bis (2-hydroxyethyl) ammonium chloride (CAS number: 94213-21-5, available from CHEMICAL LAND21 company).

Example 7

Embodiment 7 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 14, and modifier 20.

The preparation raw material of the polyurethane film for the composite fireproof glass is different from that of the polyurethane film in example 3 in that the chain extender adopts 1, 19-di (ethylene oxide) -8, 16-di (ethylene oxide methoxyl) -2,6,10,14, 18-pentaoxanonadecane-4, 12-diol (CAS number: 101377-34-8, available from Chemos GmbH company) with the same molar amount.

Example 8

Embodiment 8 provides a polyurethane film for composite fireproof glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 14, and modifier 25.

The preparation raw material of the polyurethane film for the composite fireproof glass is different from that of the polyurethane film for the example 7 in that the modifier adopts aminopropyl double-terminated polydimethylsiloxane (CAS number: 106214-84-0, purchased from Shanghai Merlin Biotech, Ltd.) with the same molar weight.

The preparation method of the polyurethane film for the composite fire-resistant glass is the same as that of the example 7.

The composite fire-resistant glass was prepared in the same manner as in example 7.

Example 9

Embodiment 9 provides a polyurethane film for composite fire-resistant glass, which is prepared from raw materials including, by weight, polyol 58, isocyanate 9.6, catalyst 0.15, chain extender 14, and modifier 25.

The preparation raw material of the polyurethane film for the composite fireproof glass is different from that of the polyurethane film in example 7 in that the modifier adopts hydroxyl-terminated polymethyl 3,3, 3-trifluoropropyl siloxane (CAS number: 68607-77-2, available from Shanghai Gillede New Material science and technology Co., Ltd.) with the same molar weight.

Comparative example 1

Comparative example 1 provides a polyurethane film for composite fire-resistant glass, which was prepared from the raw materials different from example 9 in that a modifier was not added.

The preparation method of the polyurethane film for composite fire-resistant glass is different from that of example 9 in that the third step is not included.

The composite fire-resistant glass was prepared in the same manner as in example 9.

Comparative example 2

Comparative example 2 provides a polyurethane film for composite fire-resistant glass, which is prepared from the following raw materials in difference from example 9: 1) no modifier is added; 2) the chain extender is 1, 3-propylene glycol, namely, the molecular chain does not contain epoxy groups.

Comparative example 3

Comparative example 3 provides a polyurethane film for composite fire-resistant glass, which is prepared from the raw materials that are different from those in example 8 in that the chain extender is 1, 3-propanediol, i.e., no epoxy group is contained in the molecular chain.

The preparation method of the polyurethane film for the composite fireproof glass is the same as that in the example 8, namely, the modifier and the polyurethane polymer obtained in the second step are mainly mixed in a physical blending mode.

The composite fire-resistant glass was prepared in the same manner as in example 8.

Comparative example 4

Comparative example 4 provides a polyurethane film for composite fire-resistant glass, which was prepared using the raw materials that were different from those of example 9 in that the chain extender was 1, 3-propanediol, i.e., no epoxy group was contained in the molecular chain.

The preparation method of the polyurethane film for the composite fireproof glass is the same as that of the example 9, namely, the modifier and the polyurethane polymer obtained in the second step are mainly mixed in a physical blending mode.

Evaluation of Performance

1. Testing of fire performance

According to the regulations of GB 15763.1-2001 'safety glass for buildings' fire-proof glass, the composite fire-proof glass provided in the embodiment is subjected to fire resistance test according to the national standard GB/T12513-2006, the fire resistance level of the composite fire-proof glass is divided into four levels, namely level I, level II, level III and level IV, and the corresponding fire resistance time is 90min, 60min, 45min and 30min respectively.

2. Bond Strength test

The cross method is used for measuring the interface bonding strength of the organic-inorganic composite fireproof glass on a WDW-50 type microcomputer control universal electronic testing machine, and the loading rate is 0.5 mm/min. The glass is used as a stress surface, and the stress surface is pressurized until the composite glass interface is peeled.

3. Surface contact Angle test

A certain amount of polyurethane film for composite fireproof glass is dissolved in DMSO to prepare 0.1 wt% solution, and a video optical contact angle measuring instrument (OCA 20) is used for measuring the contact angle of the polyurethane film solution on the surface of inorganic glass at room temperature (because the contact area between the middle cementing layer and the organic transparent material layer is much larger than that between the middle cementing layer and the inorganic material layer, the bonding strength problem of the middle cementing layer in the composite fireproof glass is mainly concentrated on the acting force between the middle cementing layer and the inorganic glass layer, only the contact angle of the polyurethane film solution on the surface of the inorganic glass is measured).

4. Impact strength test

A quenching steel ball with the mass of 1040g and the diameter of 63.5mm is placed at a position 1200mm from the surface of a sample, freely falls into a circle with the geometric center of the surface of the composite fireproof glass as the center and the radius of 25mm, and the damage degree of the surface of the composite fireproof glass is observed. And if the surface of the composite fireproof glass is not damaged, sequentially lifting the falling height of the steel ball to 1500mm and 1900 mm. The evaluation of the impact strength is carried out on a grade of 1-6, and the higher the score is, the stronger the impact strength is.

5. Determination of the shear Strength

The composite glass is tested by a WDW-50 type microcomputer control electronic universal tester, the shear strength is measured according to a national standard GB1450.1-83 delta beam shear test method, and the loading rate is 0.5 mm/min. The principle is as follows: directly applying pressure to the organic-inorganic composite fireproof glass until the glass interface is stripped.

TABLE 1 Performance test Table

As can be seen from Table 1, the composite fireproof glass has good fireproof performance, high impact strength and is not easy to damage when being impacted by hard objects; the polyurethane film for the composite fireproof glass has small contact angle with the surface of inorganic glass, can be fully soaked on the surface of the inorganic glass when being hot-pressed and molded with the inorganic glass and organic transparent materials, improves the contact area, thereby improving the bonding strength and the shearing strength, and is not easy to come unstuck when being stressed by stretching, shearing and the like to influence the wearability.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The polyurethane film for the composite fireproof glass is characterized by comprising, by weight, at least 50-65 parts of polyol, 7-12 parts of isocyanate, 0.1-0.2 part of catalyst, 2-14 parts of chain extender and 15-26 parts of modifier; wherein the modifier is hydroxyl-terminated polymethyl 3,3, 3-trifluoropropyl siloxane; the chain extender is selected from: 3, 4-butylene oxide-1, 2-diol, 2-bis [ (oxiranylmethoxy) methyl ] propane-1, 3-diol, 1, 19-bis (oxiranylmethoxy) -8, 16-bis (oxiranylmethoxy) -2,6,10,14, 18-pentaoxanonadecane-4, 12-diol, 2- [ (2, 3-epoxypropoxy) methyl ] -2- (hydroxymethyl) propane-1, 3-diol, or (2, 3-epoxypropyl) ethylbis (2-hydroxyethyl) ammonium chloride.

2. The polyurethane film for composite fire-resistant glass according to claim 1, wherein the catalyst is one or more selected from the group consisting of an organic butyltin catalyst, a boron trifluoride catalyst, and an amine catalyst.

3. The method for preparing the polyurethane film for the composite fire-resistant glass as claimed in claim 1 or 2, wherein the method comprises at least the following steps:

4. The composite fireproof glass is characterized by having a multi-layer structure; the multilayer structure comprises an inorganic glass layer, an organic transparent material layer and an intermediate cementing layer; the inorganic glass layer is made of inorganic float glass; the material of the organic transparent material layer is polycarbonate; the raw material of the middle cementing layer is the polyurethane film for the composite fire-proof glass as claimed in claim 1.

5. The method of making a composite fire-resistant glass according to claim 4, comprising at least the steps of: