CN113563554B - Preparation method of interlayer optical material of safety glass - Google Patents
Preparation method of interlayer optical material of safety glass Download PDFInfo
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- CN113563554B CN113563554B CN202110802387.2A CN202110802387A CN113563554B CN 113563554 B CN113563554 B CN 113563554B CN 202110802387 A CN202110802387 A CN 202110802387A CN 113563554 B CN113563554 B CN 113563554B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
Abstract
The invention discloses a preparation method of an intermediate layer optical material of safety glass. Dehydrating a part of polytetrahydrofuran in vacuum, cooling to 50-60 ℃, mixing with an antioxidant, a light stabilizer, 4' -dicyclohexylmethane diisocyanate and 0.05-0.1 part by weight of a catalyst, and reacting at 70-90 ℃ for 1-3.5 hours to obtain a prepolymer component A; dehydrating the other part of polytetrahydrofuran in vacuum, cooling to 50-60 ℃, and then uniformly mixing with micromolecular diol at 50-60 ℃ to obtain a chain extender component B; mixing the prepolymer component A with the temperature of 60-70 ℃ with the chain extender component B, and defoaming to obtain a premix; and pouring the premix into a preheated mold at 100-120 ℃ for curing for 16-28 h to obtain the intermediate layer optical material of the safety glass. The method of the invention can ensure that the mechanical property and the optical property of the interlayer optical material of the safety glass reach perfect balance.
Description
Technical Field
The invention relates to a preparation method of an interlayer optical material of safety glass.
Background
The interlayer optical material for safety glass is required to have high light transmittance and also to have excellent tensile strength. Polyvinyl butyral and ethylene-vinyl acetate copolymer can be used as the intermediate layer optical material of safety glass.
The polyurethane elastomer is a block polymer with hard blocks and soft blocks alternately arranged, and is expected to become an interlayer optical material of safety glass. The polymer polyol flexible chain forms a soft segment, and the diisocyanate and the micromolecule chain extender form a hard segment. Because the hard segments have strong polarity and strong mutual attraction force and are not compatible with the soft segments with weaker polarity in thermodynamics, the polyurethane elastomer generates a phase separation structure. The chain segment structure enables the polyurethane elastomer to have good comprehensive performance. In terms of microstructure, the mechanical properties of polyurethane elastomers are mainly due to hydrogen bonds and intermolecular and intramolecular forces generated by urethane bonds in the hard segment, which requires polyurethane molecules having a high hard segment content. However, the high polar hard segment content easily generates an ordered arrangement, thereby causing crystallization, having a distinct phase separation structure, and thus causing a decrease in light transmittance. Therefore, if the polyurethane elastomer is formed into the optical material of the interlayer of the safety glass, the transparent polyurethane elastomer needs to be designed from the level of molecular structure, so that the mechanical property and the optical property of the transparent polyurethane elastomer are perfectly balanced.
CN102250308A discloses a preparation method of a transparent elastomer, which comprises the following raw materials: (A) prepolymer component (b): diisocyanate, polyether diol and diluent, wherein the diluent is one or a mixture of more of phthalate, aliphatic diacid ester or phosphate; (B) polymer component (b): polypropylene oxide ether, catalyst and anti-aging agent; (C) and a chain extender component. The transparent elastomer has low tensile strength.
CN105175678A discloses a high-transparency polyurethane elastomer, which is mainly prepared from the following components: polyether glycol mixture, aliphatic isocyanate mixture, chain extender and maleic anhydride grafted polypropylene; wherein the polyether diol mixture is a mixture of polytetrahydrofuran ether glycol, polyoxytetramethylene glycol and polypropylene oxide glycol; the aliphatic isocyanate mixture is a mixture of hexamethylene diisocyanate and isophorone diisocyanate; the chain extender is a mixture of 1, 4-butanediol and diethylene glycol. According to the invention, the transparency and the transparency persistence of the polyurethane elastomer are improved by adjusting the dosage proportion of each component and utilizing the synergistic effect of HDI and IPDI; the mixture of 1, 4-butanediol and diethylene glycol is used as a chain extender to inhibit the crystallization of a hard section of the polyurethane elastomer, and simultaneously form a plurality of small sections, thereby increasing the surface area, effectively inhibiting the deformation of a soft section base material and improving the mechanical property. However, the highly transparent polyurethane elastomer has a high haze.
CN108047415A discloses a preparation method of optical-grade thermoplastic polyurethane elastomer. The raw materials comprise 60.00-80.00% of polyether polyol, 3.00-8.00% of polyol micromolecule chain extender, 10-30% of aliphatic diisocyanate, 0.01-0.05% of organic tin catalyst, 0.50-1.50% of oil-soluble antioxidant and 1.00-2.00% of light stabilizer, wherein the polyether polyol is selected from polytetrahydrofuran glycol with the molecular weight of 600-2000. The tensile strength of the polyurethane elastomer is 30-45MPa, the light transmittance is 85-87%, and the space for improving the light transmittance is still provided.
CN110240686A discloses a high-performance high-hardness transparent polyurethane elastomer, which comprises a prepolymer component and a curing agent component; the prepolymer component comprises polytetrahydrofuran polyol, an antioxidant, an ultraviolet absorbent and hexamethylene diisocyanate trimer; the curing agent component comprises decolorized MOCA. The light transmittance of the polyurethane elastomer is not high.
CN112794985A discloses a method for preparing a transparent polyurethane optical material, which uses isocyanate and polymer polyol as reactants, and adds additives and the like for reaction. The isocyanate is selected from 1, 4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and p-phenylene diisocyanate, the polymer polyol is selected from polytetrahydrofuran diol and polycarbonate polyol, and the additive is selected from 2, 3-bis (2-mercapto-ethylthio) -1-propyl mercaptan and 5-ethylene-propylene thio-1, 3, 4-thiadiazole-2-thiol; the accelerator is prepared by reacting polymethylhydrosiloxane with aniline substances, wherein the aniline substances are selected from 4- (10H-phenothiazin-10-yl) aniline and 4- (10H-phenothiazin-10-yl) aniline. The polyurethane material obtained by the method has higher tensile strength and hardness and higher refractive index, but the light transmittance is still to be improved. In addition, the above method requires the use of expensive thiol-based materials.
CN112126035A discloses a preparation method of a transparent high-strength thermoplastic polyurethane plate, which takes dicyclohexylmethane diisocyanate, polytetrahydrofuran ether glycol and a micromolecular chain extender as raw materials. The polyurethane board obtained by the method has low light transmittance.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing an interlayer optical material for safety glass, which designs a transparent polyurethane elastomer from a level of a molecular structure so that mechanical properties and optical properties of the transparent polyurethane elastomer are perfectly balanced. The invention achieves the above object through the following technical scheme.
The preparation method of the interlayer optical material of the safety glass comprises the following steps:
(1) dehydrating 45-53 parts by weight of polytetrahydrofuran at 110-120 ℃ for 1-3 h in vacuum, cooling to 50-60 ℃, mixing with 0.8-1.5 parts by weight of antioxidant, 0.2-2.5 parts by weight of light stabilizer, 20-40 parts by weight of 4,4' -dicyclohexylmethane diisocyanate and 0.05-0.1 part by weight of catalyst, and reacting at 70-90 ℃ for 1-3.5 h to obtain a prepolymer component A;
(2) dehydrating 13-20 parts by weight of polytetrahydrofuran at 110-120 ℃ for 1-3 h in vacuum, then cooling to 50-60 ℃, and then uniformly mixing with 5-13 parts by weight of micromolecular diol at 50-60 ℃ to obtain a chain extender component B;
(3) mixing the prepolymer component A with the temperature of 60-70 ℃ with the chain extender component B, and defoaming to obtain a premix; pouring the premix into a preheated mold at 100-120 ℃ and curing for 16-28 h to obtain the intermediate layer optical material of the safety glass;
wherein the micromolecule diol is a mixture of micromolecule diol A containing a carbamate bond and alkane micromolecule diol B containing 1-6 carbon atoms, and the micromolecule diol A containing the carbamate bond has a structure shown in the following formula (I)
In the formula, n is a natural number of 2-10; r is selected from hydrogen or C1-C6 alkyl.
According to the production method of the present invention, preferably, the polytetrahydrofuran of the step (1) and the step (2) is polytetrahydrofuran ether glycol having no substituent.
According to the preparation method of the invention, preferably, the antioxidant is selected from one or more of IRGANOX PS800, IRGANOX 245, IRGANOX 1010 and IRGANOX 1076.
According to the preparation method of the invention, preferably, the light stabilizer is one or more of UV292, UV328, UV329, UV531, UV5411 and UV 123; the catalyst is selected from one of organic tin, organic bismuth, organic lead and organic zinc.
According to the preparation method of the invention, preferably, the alkyl of C1-C6 is methyl or ethyl.
According to the production method of the present invention, preferably, the urethane bond-containing small molecule diol a is obtained by a ring-opening reaction of ethylene carbonate and an alkanyl small molecule diamine.
According to the preparation method of the invention, preferably, the alkane-based small molecular diol B containing 1-6 carbon atoms is selected from one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
According to the preparation method of the invention, preferably, the content of the small molecular diol A containing the urethane bond is 75-85 wt%, and the content of the alkane-based small molecular diol B containing 1-6 carbon atoms is 15-25 wt%.
According to the preparation method of the invention, the number average molecular weight of the polytetrahydrofuran is preferably 1000-3000.
According to the preparation method of the invention, preferably, the tensile strength of the interlayer optical material of the safety glass is more than 39MPa, the Shore hardness is more than 68, the light transmittance is more than or equal to 90%, and the haze is less than or equal to 0.8%.
The mixture of micromolecular diol containing a urethane bond and alkane diol is used as a chain extender, and polytetrahydrofuran and 4,4' -dicyclohexylmethane diisocyanate are used as main raw materials, so that the interlayer optical material of the safety glass with remarkably reduced haze can be obtained. In addition, the formula and the process can also ensure that the intermediate layer optical material of the safety glass has higher tensile strength, hardness and light transmittance. Thus, the mechanical property and the optical property of the interlayer optical material of the safety glass are perfectly balanced.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The safety glass of the invention is a kind of glass which can not be broken by violent vibration or impact and can not hurt people even if broken. The safety glass is used for doors and windows of automobiles, airplanes and special buildings. Safety glass is typically formed from two layers of toughened glass with an interlayer of optical material sandwiched between them. Currently, the interlayer optical material is generally formed of polyvinyl butyral, ethylene-vinyl acetate copolymer. The interlayer optical material of the safety glass obtained by the method has both mechanical property and optical property, and is expected to replace the existing interlayer optical material of the safety glass.
The preparation method of the interlayer optical material of the safety glass comprises the following steps: (1) preparing a prepolymer component A; (2) a step of preparing a chain extender component B; (3) and (3) preparing the intermediate layer optical material. As described in detail below.
Preparation of prepolymer component A
And (2) dehydrating a part of polytetrahydrofuran in vacuum, cooling, mixing with an antioxidant, a light stabilizer, 4' -dicyclohexylmethane diisocyanate and a catalyst, and reacting to obtain a prepolymer component A. In some embodiments, 45-53 parts by weight of polytetrahydrofuran is subjected to vacuum dehydration at 110-120 ℃ for 1-3 hours, then the temperature is reduced to 50-60 ℃, and then the polytetrahydrofuran is mixed with 0.8-1.5 parts by weight of antioxidant, 0.2-2.5 parts by weight of light stabilizer, 20-40 parts by weight of 4,4' -dicyclohexylmethane diisocyanate and 0.05-0.1 part by weight of catalyst, and the mixture is reacted at 70-90 ℃ for 1-3.5 hours to obtain a prepolymer component A.
The polytetrahydrofuran of the invention is preferably polytetrahydrofuran ether glycol which carries no substituents. The present inventors have found that when polytetrahydrofuran has a substituent, the main chain extender (urethane bond-containing small molecule diol a) of the present invention does not function sufficiently. The polytetrahydrofuran derivative has important influence on the mechanical property and the optical property of the interlayer optical material of the safety glass. The interlayer optical material of the safety glass with lower haze can be obtained by combining Polytetrahydrofuran (PTMEG) with the small molecular diol A containing the urethane bond; however, when a polytetrahydrofuran derivative such as trimethylpolytetrahydrofuran is used in combination with the urethane bond-containing small-molecular diol A of the present invention, an interlayer optical material of safety glass having low haze cannot be obtained. In the step of preparing the prepolymer component a, the amount of polytetrahydrofuran is 45 to 53 parts by weight, preferably 45 to 49 parts by weight, and more preferably 45 to 46 parts by weight. The polytetrahydrofuran is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are both considered, and particularly, the influence on the haze is large.
The polytetrahydrofuran of the invention has a number average molecular weight of 1000 to 3000, preferably 1200 to 2500, more preferably 2000 to 2300. The number average molecular weight can be measured by GPC. The molecular weight of the polytetrahydrofuran has certain influence on the mechanical property and the optical property of the interlayer optical material of the safety glass. The molecular weight of the polytetrahydrofuran is lower than 1000, and the interlayer optical material of the obtained safety glass has higher tensile strength but higher haze. The molecular weight of the polytetrahydrofuran is higher than 3000, the tensile strength of the interlayer optical material of the safety glass is lower, and the haze is higher. By controlling the molecular weight of the polytetrahydrofuran within the range of the invention, the interlayer optical material of the safety glass has moderate tensile strength and low haze.
The polytetrahydrofuran is dehydrated in vacuum and then cooled to obtain the dehydrated polytetrahydrofuran. The temperature of the vacuum dehydration can be 110-120 ℃, preferably 112-119 ℃, and more preferably 115-118 ℃. The vacuum dehydration time can be 1-3 h, preferably 1.5-3 h, and more preferably 2-2.5 h. Therefore, the moisture of the polytetrahydrofuran can be fully removed, side reactions are reduced, and the mechanical property and the optical property of the intermediate layer optical material of the safety glass are improved. The temperature of the dehydrated polytetrahydrofuran is kept between 50 and 60 ℃, preferably between 55 and 60 ℃, so that the subsequent reaction is facilitated, and the energy consumption is saved.
The dehydrated polytetrahydrofuran is mixed with an antioxidant, a light stabilizer, 4' -dicyclohexylmethane diisocyanate and a catalyst, and then reacted to form a prepolymer component A.
The antioxidant of the present invention may be selected from one or more of IRGANOX PS800, IRGANOX 245, IRGANOX 1010, IRGANOX 1076. IRGANOX PS800 may also be referred to as Pasteur antioxidant Irganox PS800 (DLTP). IRGANOX 245 is a hindered phenolic antioxidant which is ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ]. IRGANOX 1076 is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. In certain embodiments, the antioxidant of the present invention is IRGANOX 1010, i.e., pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]. The antioxidant is used in an amount of 0.8 to 1.5 parts by weight, preferably 0.9 to 1.3 parts by weight, and more preferably 1 to 1.2 parts by weight. The antioxidant is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are both considered. Too large an amount of antioxidant may result in an increase in haze of the material.
The light stabilizer of the invention can be one or more of UV292 (bis (1,2,2,6, 6-pentamethylpiperidyl) -sebacate), UV328((2' -hydroxy-3 ',5' -ditert-pentylphenyl) benzotriazole), UV329(2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole), UV531 (benzophenone-12; 2-hydroxy-4-n-octyloxybenzophenone), UV5411(2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole) and UV123 (bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidine) sebacate). In certain embodiments, the light stabilizer of the present invention is UV123, i.e., bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidine) sebacate. The amount of the light stabilizer is 0.2 to 2.5 parts by weight, preferably 0.3 to 2 parts by weight, and more preferably 0.5 to 1 part by weight. The light stabilizer is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are favorably considered. Too large an amount of light stabilizer may result in an increase in haze of the material. The invention adopts 4,4' -dicyclohexyl methane diisocyanate as isocyanate. The isocyanate includes Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI), cyclohexanedimethylene diisocyanate (HXDI), and the like. The invention discovers that the interlayer optical material of the safety glass with lower haze can be obtained by combining HMDI with polytetrahydrofuran and the small molecular diol A containing the urethane bond. The amount of 4,4' -dicyclohexylmethane diisocyanate is 20 to 40 parts by weight, preferably 25 to 35 parts by weight, and more preferably 28 to 30 parts by weight. The 4,4' -dicyclohexylmethane diisocyanate is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are favorably considered. Too much 4,4' -dicyclohexylmethane diisocyanate is used, and although the hardness of the material increases, the haze may also increase; the use amount of 4,4' -dicyclohexylmethane diisocyanate is too small, and the mechanical property of the material is poor.
The catalyst of the invention can be selected from one of organic tin, organic bismuth, organic lead and organic zinc; organotin is preferred. Examples of organotin include, but are not limited to, dibutyltin dilaurate, i.e., T12. The catalyst is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are both considered.
The reaction temperature for forming the prepolymer component A can be 70-90 ℃, preferably 75-86 ℃, and more preferably 82-85 ℃. The reaction time is 1-3.5 h, preferably 1.5-3 h, and more preferably 2-3 h. Under the conditions, the system of the prepolymer component A is relatively stable.
Preparation step of chain extender component B
And (3) dehydrating the other part of polytetrahydrofuran in vacuum, cooling, and uniformly mixing with the micromolecular diol to obtain the chain extender component B. In some embodiments, 13 to 20 parts by weight of polytetrahydrofuran is dehydrated in vacuum at 110 to 120 ℃ for 1 to 3 hours, then cooled to 50 to 60 ℃, and then uniformly mixed with 5 to 13 parts by weight of small molecular diol at 50 to 60 ℃ to obtain the chain extender component B.
The polytetrahydrofuran of the invention is preferably polytetrahydrofuran ether glycol which carries no substituents. The present inventors have found that when polytetrahydrofuran has a substituent, the main chain extender (urethane bond-containing small molecule diol a) of the present invention does not function sufficiently. The polytetrahydrofuran derivative has important influence on the mechanical property and the optical property of the interlayer optical material of the safety glass. The interlayer optical material of the safety glass with lower haze can be obtained by combining Polytetrahydrofuran (PTMEG) with the small molecular diol A containing the urethane bond; however, when a polytetrahydrofuran derivative such as trimethylpolytetrahydrofuran is used in combination with the urethane bond-containing small-molecular diol A of the present invention, an interlayer optical material of safety glass having low haze cannot be obtained. In the step of preparing the chain extender component B, the amount of polytetrahydrofuran is 13 to 20 parts by weight, preferably 15 to 18 parts by weight, and more preferably 15 to 16 parts by weight. The polytetrahydrofuran is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are both considered, and particularly, the influence on the haze is large.
The polytetrahydrofuran of the invention has a number average molecular weight of 1000 to 3000, preferably 1200 to 2500, more preferably 2000 to 2300. The number average molecular weight can be measured by GPC. The molecular weight of the polytetrahydrofuran has certain influence on the mechanical property and the optical property of the interlayer optical material of the safety glass. The molecular weight of the polytetrahydrofuran is lower than 1000, and the interlayer optical material of the obtained safety glass has higher tensile strength but higher haze. The molecular weight of the polytetrahydrofuran is higher than 3000, the tensile strength of the interlayer optical material of the safety glass is lower, and the haze is higher. By controlling the molecular weight of the polytetrahydrofuran within the range of the invention, the interlayer optical material of the safety glass has moderate tensile strength and low haze.
The polytetrahydrofuran is dehydrated in vacuum and then cooled to obtain the dehydrated polytetrahydrofuran. The temperature of the vacuum dehydration can be 110-120 ℃, preferably 112-119 ℃, and more preferably 115-118 ℃. The vacuum dehydration time can be 1-3 h, preferably 1.5-3 h, and more preferably 2-2.5 h. Therefore, the moisture of the polytetrahydrofuran can be fully removed, side reactions are reduced, and the mechanical property and the optical property of the intermediate layer optical material of the safety glass are improved. The temperature of the dehydrated polytetrahydrofuran is kept between 50 and 60 ℃, preferably between 55 and 60 ℃, so that the subsequent reaction is facilitated, and the energy consumption is saved.
It should be noted that the vacuum dehydration processes of polytetrahydrofuran in step (1) and step (2) may be performed synchronously in the same vessel, synchronously in different vessels, or asynchronously in different vessels.
And uniformly mixing the dehydrated polytetrahydrofuran and the micromolecule diol to obtain a chain extender component B. The mixing temperature may be 50 to 60 ℃, preferably 55 to 60 ℃.
The amount of the small molecular diol used in the present invention may be 5 to 13 parts by weight, preferably 6 to 10 parts by weight, and more preferably 7 to 9 parts by weight. The small molecular diol is controlled in the range, so that the mechanical property and the optical property of the interlayer optical material of the safety glass are both considered, and particularly the haze is greatly influenced.
The micromolecular diol is a mixture of micromolecular diol A containing a carbamate bond and chain alkyl micromolecular diol B containing 1-6 carbon atoms. The content of the small molecular diol A containing the urethane bond is 75-85 wt%, preferably 77-83 wt%, and preferably 80-82 wt%. The content of the chain alkyl small molecular diol B containing 1 to 6 carbon atoms is 15 to 25 wt%, preferably 18 to 23 wt%, and preferably 20 to 22 wt%. Thus, the mechanical property and the optical property of the interlayer optical material of the safety glass can be considered at the same time. Compared with the common chain alkyl dihydric alcohol (such as 1, 4-butanediol), the small molecular diol A containing the urethane bond is used as the main chain extender, and under the condition that the charging amount of isocyanate is consistent, the number of the urethane bond in a polyurethane molecular chain segment and the length of a hard segment are increased, so that the hydrogen bond and intermolecular force of the polyurethane molecular chain are enhanced, and the phase separation degree of the hard segment and a soft segment is better, thereby showing better mechanical property. However, the use of the urethane bond-containing small-molecule diol A in an excessively large amount results in a reduction in the haze of the material.
The small molecular diol A containing the urethane bond has a structure shown as the following formula (I)
In the formula, n is a natural number of 2-10; r is selected from hydrogen or C1-C6 alkyl.
In the present invention, n is preferably a natural number of 3 to 8, and more preferably a natural number of 4 to 6. Examples of C1-C6 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like. In certain embodiments, the C1-C6 alkyl group is methyl or ethyl. Specific examples of the urethane bond-containing small-molecule diol A of the present invention include, but are not limited to, 1, 6-bis (2-hydroxyethylethoxycarbonylamino) butane.
The urethane bond-containing small molecule diol A can be obtained by the ring-opening reaction of ethylene carbonate and chain alkyl small molecule diamine. These reaction conditions are conventional and will not be described in detail here.
The alkane-based small molecular diol B containing 1-6 carbon atoms can be one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol and 1, 6-hexanediol. Preferably, the chain alkyl small molecular diol B containing 1-6 carbon atoms is selected from one of 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 3-butanediol. More preferably, the chain alkyl small molecular diol B containing 1-6 carbon atoms is 1, 4-butanediol or 1, 3-butanediol.
The mixture of the micromolecular diol A containing the urethane bond and the chain alkyl micromolecular diol B containing 1-6 carbon atoms is used as the chain extender, so that the haze of the polyurethane elastomer can be effectively reduced. In addition, the chain extender component B also comprises polytetrahydrofuran. On one hand, the viscosity of the prepolymer component A and the viscosity of the chain extender component B are similar, and the prepolymer component A and the chain extender component B are mixed more uniformly; on the other hand, the reaction speed can be adjusted, and the problems that the viscosity is increased too fast after mixing and the processing is difficult are avoided. Experiments show that the polytetrahydrofuran is also favorable for adjusting the structure of the polyurethane elastomer and improving the performance of the interlayer optical material of the safety glass.
Preparation step of interlayer optical material
Mixing the prepolymer component A and the chain extender component B, and defoaming to obtain a premix; and pouring the premix into a preheating mould for curing to obtain the intermediate layer optical material of the safety glass. In some embodiments, the prepolymer component A and the chain extender component B at the temperature of 60-70 ℃ are mixed and defoamed to obtain a premix; and pouring the premix into a preheated mold at 100-120 ℃ for curing for 16-28 h to obtain the intermediate layer optical material of the safety glass. The temperature of the prepolymer component A can be 60-70 ℃, preferably 60-65 ℃, and more preferably 60-63 ℃. The deaeration can be carried out by conventional methods, which will not be described herein. The temperature of the mold can be 100-120 ℃, preferably 100-110 ℃, and more preferably 100-105 ℃. The curing time can be 16-28 h, preferably 20-25 h, and more preferably 22-24 h.
The tensile strength of the optical material of the interlayer of the safety glass prepared by the method is more than 39MPa, preferably 39-50 MPa, and more preferably 43-49 MPa. The Shore hardness is greater than 68, preferably 68-75, and more preferably 70-73. The light transmittance is 90% or more, preferably 91% or more. The haze is 0.8% or less, preferably 0.7% or less. Tensile strength was tested using GB/T528-2009. The light transmittance and the haze are tested by GB/T2410-2008.
Example 1 and comparative example 1
The raw material formula for preparing the interlayer optical material of the safety glass is as follows:
according to the formula, the interlayer optical material of the safety glass is prepared by the following method:
(1) dehydrating 45.3 parts by weight of polytetrahydrofuran at 110 ℃ for 2h in vacuum, then cooling to 60 ℃, adding IRGANOX 1010, UV123, 4' -dicyclohexylmethane diisocyanate and T12 according to the proportion, stirring and heating, and reacting at 80 ℃ for 3h to obtain a prepolymer component A;
(2) dehydrating 15.1 parts by weight of polytetrahydrofuran at 110 ℃ for 2h in vacuum, then cooling to 60 ℃, adding small molecular diol (see table 1) according to the proportion, and stirring at 60 ℃ to uniformly mix the small molecular diol to obtain a chain extender component B;
(3) and cooling the prepolymer component A to 70 ℃, adding the chain extender component B, stirring and defoaming to obtain the premix. And pouring the premix into a preheated mold at 100 ℃ for curing for 24 hours to obtain the interlayer optical material of the safety glass.
Example 2 and comparative example 2
The raw material formula for preparing the interlayer optical material of the safety glass is as follows:
according to the formula, the interlayer optical material of the safety glass is prepared by the following method:
(1) 47.775 parts by weight of polytetrahydrofuran is dehydrated for 2 hours in vacuum at 110 ℃, then the temperature is reduced to 55 ℃, IRGANOX 1010, UV123, 4' -dicyclohexylmethane diisocyanate and T12 are added according to the proportion, the mixture is stirred and heated, and the mixture reacts for 3 hours at 85 ℃ to obtain a prepolymer component A;
(2) 15.925 parts by weight of polytetrahydrofuran is dehydrated for 2 hours in vacuum at 110-120 ℃, then the temperature is reduced to 55 ℃, micromolecular diol (see table 1) is added according to the proportion amount, and the mixture is stirred at 60 ℃ to be uniformly mixed, so that a chain extender component B is obtained;
(3) and cooling the prepolymer component A to 65 ℃, adding the chain extender component B, and stirring and defoaming to obtain the premix. And pouring the premix into a preheated mold at 110 ℃ for curing for 24h to obtain the interlayer optical material of the safety glass.
Example 3 and comparative example 3
The raw material formula for preparing the interlayer optical material of the safety glass is as follows:
according to the formula, the interlayer optical material of the safety glass is prepared by the following method:
(1) dehydrating 51.9 parts by weight of polytetrahydrofuran at 120 ℃ for 2h in vacuum, then cooling to 50 ℃, adding IRGANOX 1010, UV123, 4' -dicyclohexylmethane diisocyanate and T12 according to the proportion, stirring and heating, and reacting at 80 ℃ for 3h to obtain a prepolymer component A;
(2) dehydrating 17.3 parts by weight of polytetrahydrofuran at 20 ℃ for 2h in vacuum, then cooling to 50 ℃, adding small molecular diol (see table 1) according to the proportion, and stirring at 50 ℃ to uniformly mix the small molecular diol to obtain a chain extender component B;
(3) and cooling the prepolymer component A to 60 ℃, adding the chain extender component B, stirring and defoaming to obtain the premix. And pouring the premix into a preheated mold at 100 ℃ for curing for 24 hours to obtain the interlayer optical material of the safety glass.
Comparative example 4
Except that the polytetrahydrofuran PTMEG (molecular weight 2000) of example 2 was replaced with trimethyl polytetrahydrofuran (molecular weight 2000, trade name:
3MCPG2100), the rest is the same as in example 2.
Comparative example 5
Except that polytetrahydrofuran PTMEG (molecular weight 2000) of comparative example 2 was replaced with trimethyl polytetrahydrofuran (molecular weight 2000, trade name:
3MCPG2100), the rest is the same as in comparative example 2.
TABLE 1
| Numbering | Small molecule diols |
| Example 1 | Mixture of 80% by weight of 1, 6-bis (2-hydroxyethylethoxycarbonylamino) butane and 20% by weight of 1, 4-butanediol |
| Comparative example 1 | 1, 4-butanediol |
| Example 2 | Mixture of 80% by weight of 1, 6-bis (2-hydroxyethylethoxycarbonylamino) butane and 20% by weight of 1, 4-butanediol |
| Comparative example 2 | 1, 4-butanediol |
| Example 3 | Mixture of 80% by weight of 1, 6-bis (2-hydroxyethylethoxycarbonylamino) butane and 20% by weight of 1, 4-butanediol |
| Comparative example 3 | 1, 4-butanediol |
The structural formula of the 1, 6-bis (2-hydroxyethyl ethoxycarbonylamino) butane is shown in the specification
The interlayer optical material (2mm thick) of the safety glass is cut into standard sample strips by an elastomer pneumatic sheet punching machine, and the tensile property test is carried out by GB/T528-2009. An optical test sample sheet is prepared by laminating the interlayer optical material (2mm thick) of the safety glass and inorganic glass, and the light transmittance and haze test is carried out by adopting GB/T2410-2008. The test results are shown in Table 2.
TABLE 2
The above table shows that the specific small molecular diol of the invention can significantly improve the tensile strength of the interlayer optical material of the safety glass, the shore hardness is slightly improved, the light transmittance is significantly improved, and the haze is greatly reduced. Therefore, the method of the invention can ensure that the mechanical property and the optical property of the interlayer optical material of the safety glass are perfectly balanced.
From examples 1 to 3, it is clear that the molecular weight of polytetrahydrofuran has a certain influence on the mechanical and optical properties of the interlayer optical material of safety glass. The molecular weight of the polytetrahydrofuran of example 1 is 1000, and the interlayer optical material of the resulting safety glass has high tensile strength but also high haze. The molecular weight of the polytetrahydrofuran of example 3 is 3000, the tensile strength of the interlayer optical material of safety glass is low, and the haze is high. The molecular weight of the polytetrahydrofuran of example 2 is 2000, the tensile strength of the interlayer optical material of safety glass is moderate, and the haze is low.
Comparing example 2 with comparative example 4, it is found that the type of polytetrahydrofuran derivative also has an important influence on the mechanical properties and optical properties of the interlayer optical material of safety glass. Example 2 interlayer optical materials of safety glass with lower haze can be obtained using Polytetrahydrofuran (PTMEG) in combination with certain small molecule diols of the present invention. Comparative example 4 using trimethyl polytetrahydrofuran in combination with the specific small molecule diol of the present invention, an interlayer optical material of safety glass having low haze could not be obtained.
Comparing comparative example 4 with comparative example 5, it was found that the combination of trimethylpolytetrahydrofuran and the specific small-molecular diol of the present invention can improve the tensile strength of the interlayer optical material of safety glass, but cannot improve the haze and the light transmittance of the interlayer optical material of safety glass.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (7)
1. A preparation method of an interlayer optical material of safety glass is characterized by comprising the following steps:
(1) dehydrating 45-53 parts by weight of polytetrahydrofuran at 110-120 ℃ for 1-3 h in vacuum, cooling to 50-60 ℃, mixing with 1-1.5 parts by weight of antioxidant, 0.2-2.5 parts by weight of light stabilizer, 20-40 parts by weight of 4,4' -dicyclohexylmethane diisocyanate and 0.05-0.1 part by weight of catalyst, and reacting at 70-90 ℃ for 1-3.5 h to obtain a prepolymer component A;
(2) dehydrating 13-20 parts by weight of polytetrahydrofuran at 110-120 ℃ for 1-3 h in vacuum, then cooling to 50-60 ℃, and then uniformly mixing with 5-13 parts by weight of micromolecular diol at 50-60 ℃ to obtain a chain extender component B;
(3) mixing the prepolymer component A with the temperature of 60-70 ℃ with the chain extender component B, and defoaming to obtain a premix; pouring the premix into a preheated mold at 100-120 ℃ and curing for 16-28 h to obtain the intermediate layer optical material of the safety glass;
wherein the micromolecule diol is a mixture of micromolecule diol A containing a carbamate bond and alkane micromolecule diol B containing 1-6 carbon atoms, and the micromolecule diol A containing the carbamate bond has a structure shown in the following formula (I)
In the formula, n is a natural number of 2-10; r is selected from hydrogen or alkyl of C1-C6;
in the small molecular diol, the content of the small molecular diol A containing a urethane bond is 75-85 wt%, and the content of the alkane-based small molecular diol B containing 1-6 carbon atoms is 15-25 wt%;
wherein the polytetrahydrofuran in the step (1) and the step (2) is polytetrahydrofuran ether glycol without substituent groups, and the number average molecular weight of the polytetrahydrofuran is 1000-3000.
2. The method of claim 1, wherein the antioxidant is selected from one or more of IRGANOX PS800, IRGANOX 245, IRGANOX 1010, and IRGANOX 1076.
3. The preparation method according to claim 1, wherein the light stabilizer is one or more of UV292, UV328, UV329, UV531, UV5411 and UV 123; the catalyst is selected from one of organic tin, organic bismuth, organic lead and organic zinc.
4. The method according to claim 1, wherein the alkyl group having 1 to 6 is a methyl group or an ethyl group.
5. The method according to claim 1, wherein the urethane bond-containing small molecule diol A is obtained by a ring-opening reaction of ethylene carbonate with an alkanyl small molecule diamine.
6. The method according to claim 1, wherein the alkane-based small-molecule diol B having 1 to 6 carbon atoms is one or more selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.
7. The preparation method according to any one of claims 1 to 6, wherein the tensile strength of the safety glass interlayer optical material is greater than 39MPa, the Shore hardness is greater than 68, the light transmittance is greater than or equal to 90%, and the haze is less than or equal to 0.8%.
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| CN101760143A (en) * | 2009-12-22 | 2010-06-30 | 广州鹿山新材料股份有限公司 | Highly-transparent polyurethane hot-melt film applicable to sandwich glass and preparation method thereof |
| CN108047415A (en) * | 2018-01-10 | 2018-05-18 | 中国航发北京航空材料研究院 | A kind of optical grade thermoplastic polyurethane elastomer and preparation method thereof |
| CN112794985A (en) * | 2020-12-30 | 2021-05-14 | 温州大学新材料与产业技术研究院 | Transparent polyurethane optical material and preparation method thereof |
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| CN101492524A (en) * | 2008-01-25 | 2009-07-29 | 拜尔材料科学股份公司 | Transparent thermoplastic polyurethane with low haze and good processability, preparation method and application thereof |
| CN101760143A (en) * | 2009-12-22 | 2010-06-30 | 广州鹿山新材料股份有限公司 | Highly-transparent polyurethane hot-melt film applicable to sandwich glass and preparation method thereof |
| CN108047415A (en) * | 2018-01-10 | 2018-05-18 | 中国航发北京航空材料研究院 | A kind of optical grade thermoplastic polyurethane elastomer and preparation method thereof |
| CN112794985A (en) * | 2020-12-30 | 2021-05-14 | 温州大学新材料与产业技术研究院 | Transparent polyurethane optical material and preparation method thereof |
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