WO2022242167A1

WO2022242167A1 - Polyurethane having anti-ultraviolet performance and preparation method therefor

Info

Publication number: WO2022242167A1
Application number: PCT/CN2021/139968
Authority: WO
Inventors: 陈登龙; 吴丹丹; 刘金玲; 刘志鹏; 林金火; 雷自强
Original assignee: 福建师范大学泉港石化研究院
Priority date: 2021-05-17
Filing date: 2021-12-21
Publication date: 2022-11-24
Also published as: CN113214637A

Abstract

The present invention relates to the technical field of polyurethane polymer materials. Specifically disclosed are polyurethane having anti-ultraviolet performance and a preparation method therefor. In the present invention, triisopropyl borate, dihydric alcohol, and triatomic alcohol are used as raw materials, and a catalyst is added to prepare a chelating borate ester coupling agent containing a dihydroxy functional group, then the surface of a nano rare earth oxide is modified by using the chelating borate ester coupling agent containing the dihydroxy functional group to obtain a modified nano rare earth oxide, and in-situ polymerization is performed on the modified nano rare earth oxide and a polyester polyol or polyether polyol, polyisocyanate and a chain extender to obtain the polyurethane having the anti-ultraviolet performance. The polyurethane obtained in the present invention has a more durable, more stable and excellent anti-ultraviolet performance.

Description

A kind of polyurethane with anti-ultraviolet performance and preparation method thereof

technical field

The invention belongs to the technical field of polyurethane polymer materials, and in particular relates to a polyurethane with anti-ultraviolet performance and a preparation method thereof.

Background technique

As a polymer material with excellent performance, polyurethane (PU) is widely used in many fields such as automobile manufacturing, transportation, clothing, petrochemical industry, aerospace and so on. However, ordinary PU materials are prone to aging, degradation and yellowing under the action of light and heat, especially ultraviolet light, which affects both product performance and appearance. To solve this problem, a UV shielding agent or the like is usually added.

Commonly used ultraviolet shielding agents mainly include TiO ₂ and ZnO, etc., which are favored by people because of their excellent properties such as non-toxicity and stability. However, ZnO has high photocatalytic activity and insufficient absorption capacity on the short-wavelength side, while for TiO ₂ , although its forbidden band width reaches 3.2eV, its refractive index n is close to 2.7, and it is incorporated into polyurethane resin It will affect the color and transparency of the product. Moreover, the application of nanoparticles such as TiO ₂ and ZnO with anti-ultraviolet function to polyurethane resin still has problems such as easy agglomeration and insufficient stability. The general solution to these problems is to add conventional surfactants, which can eliminate the surface charge of the nanoparticles and enhance the lipophilicity of the nanoparticles, so that the nanoparticles can be doped into the polyurethane resin, but this makes The combination of nanoparticles and polyurethane, its stability and dispersibility are still not good enough, so that the anti-ultraviolet performance of the polyurethane resin is greatly reduced; and some nanoparticles with anti-ultraviolet function will also affect the material itself after being combined with polyurethane. color.

Therefore, it has become an urgent problem to find a kind of nanoparticle with anti-ultraviolet function suitable for polyurethane, and to combine the anti-ultraviolet functional nanoparticle suitable for polyurethane with polyurethane resin more stably and uniformly.

technical problem

How to solve the problem of high dispersion of nano-rare earth oxides in polyurethane matrix, so as to further improve the anti-ultraviolet performance of materials.

technical solution

The object of the present invention is to provide a polyurethane with anti-ultraviolet performance, and the polyurethane material has more durable, stable and excellent anti-ultraviolet performance.

The above object of the present invention is achieved through the following technical scheme: a kind of polyurethane with anti-ultraviolet performance, using triisopropyl borate, dihydric alcohol and trihydric alcohol as raw materials and adding a catalyst, and controlling the reaction parameters to prepare a polyurethane containing bis A chelating borate coupling agent with a hydroxyl functional group, and then using the chelating borate coupling agent containing a dihydroxy functional group to modify the surface of the nano-rare earth oxide to obtain a modified nano-rare earth oxide The modified nano-rare earth oxide, polyisocyanate, chain extender, polyester polyol or polyether polyol is used as raw materials to carry out in-situ polymerization to obtain the polyurethane with anti-ultraviolet performance.

Further, the nano rare earth oxide is one or both of nano rare earth cerium oxide and nano rare earth lanthanum oxide.

Further, the catalyst is one or both of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, and potassium tert-butoxide.

Further, the molar ratio of triisopropyl borate, diol and triol is 1:1-1.05:1-1.05.

Further, the dihydric alcohol is one of ethylene glycol, propylene glycol and butanediol.

Further, the trihydric alcohol is one of glycerol and trimethylolpropane.

Further, the mass ratio of the nanometer rare earth oxide to the chelating borate coupling agent of the dihydroxy functional group is 100:0.1-5.

Using the above technical scheme, the 4f electrons of nano-rare earth oxides have no absorption for visible light, but show excellent absorption capacity for ultraviolet light. The combination of nano-rare earth oxides and polyurethane not only makes the final polyurethane material have good UV resistance, but also And it will not affect the original color of the polyurethane material.

Utilize the interaction between triisopropyl borate, dibasic alcohol and tribasic alcohol to synthesize the chelating type borate coupling agent containing dihydroxy functional group, then utilize the chelating type coupling agent containing dihydroxy functional group The borate coupling agent is used to modify the surface of nano-rare earth oxides, and then the modified nano-rare earth oxides are used as reactive monomers for in-situ polymerization with polyester polyol or polyether polyol, polyisocyanate, and chain extenders The reaction makes the nano-rare earth oxides more stable and firmly locked in the polyurethane matrix, so that the finally obtained polyurethane has more durable and excellent UV resistance.

Another object of the present invention is to provide a method for preparing polyurethane with UV resistance, which has the advantages of convenient and simple operation.

Above-mentioned purpose of the present invention is achieved by following technical scheme: a kind of preparation method of polyurethane with anti-ultraviolet performance, prepares according to following steps:

S1. In a three-necked flask with a thermometer, a stirrer, and a reflux condenser, add triisopropyl borate and a catalyst, then raise the temperature to 80-130°C, and add glycol dropwise under constant stirring, and heat to reflux for 60- After 120 minutes, add the measured trihydric alcohol, continue the reflux reaction at 130-180°C for 90-150 minutes, and distill the isopropanol under reduced pressure to obtain a chelating borate coupling agent containing dihydroxy functional groups ;

S2. Dry the nano-rare earth oxide at 105°C for 1-4 hours, and then add it to the chelating type borate coupling agent containing dihydroxy functional groups prepared in S1 in proportion and heat it up to 115-140°C React in a high-mixer for 15-60 minutes, and obtain modified nano-rare earth oxides after cooling;

S3. In parts by weight, heat and melt 100 parts of dehydrated polyester polyol or polyether polyol, 0.1-5 parts of modified nano-rare earth oxide, 0.1-1 part of antioxidant, and 0.1-1 part of lubricant Mix uniformly to obtain the first mixture; accurately add the first mixture, 50-150 parts of polyisocyanate, and 0.5-5 parts of chain extender to a twin-screw extrusion granulator at 100°C through a metering pump, and Melt blending and in-situ polymerization at 200° C., extruding strands, drying and pelletizing to obtain the polyurethane with UV resistance.

Further, the polyester polyol is adipic acid polyester diol, polycarbonate diol, phthalic anhydride polyester diol, polycaprolactone diol, succinic acid polyester diol, glutaric acid Polyester diol, azelaic acid polyester diol, dodecanedioic acid polyester diol, 1,4-cyclohexanedicarboxylic acid polyester diol, dimer acid polyester diol, mixed diacid polyester One or more of diol, terephthalic acid polyester diol, polymer polyester diol, isophthalic acid polyester diol, and trimellitic acid polyester polyol.

Further, the polyether polyol is polytetrahydrofuran diol, polyoxypropylene diol, tetrahydrofuran-oxypropylene copolymerized diol, polyoxypropylene-oxyethylene diol, polyoxyethylene diol, polytrimethylene ether diol Alcohol, highly reactive polyether diol, aniline polyether diol, phenol polyether diol, substituted aniline polyether diol, bisphenol A/ethylene oxide polyether diol, bisphenol A/propylene oxide polyether diol, One or more of propylene glycol block polyethers.

Further, the polyisocyanate is 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate, naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), dimethyl biphenyl diisocyanate (TODI), polyphenyl polymethylene polyisocyanate (PAPI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), xylylene diisocyanate (XDI), tetramethyl-m-xylylene diisocyanate (TMXDI), 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexyl diisocyanate ( HTDI), cyclohexane dimethylene diisocyanate (HXDI), norbornane diisocyanate (NBDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI) one or more.

Further, the chain extender is one or more of ethylene glycol, 1,4-butanediol, 1,3-propanediol, ethanolamine, and diethyltoluenediamine.

Further, the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite.

Further, the lubricant is ethylene bisoleic acid amide.

Beneficial effect

The present invention has the following beneficial effects:

1. The chelating boric ester coupling agent containing double hydroxyl functional groups modifies the nano-rare earth oxides to obtain modified nano-rare earth oxides, and then uses the modified nano-rare earth oxides as reaction monomers to react with polyester polyols Or polyether polyols, polyisocyanates and other substances undergo in-situ polymerization reactions, making the combination of nano-rare earth oxides and polyurethane matrix more uniform, stable and firm, and making the UV resistance of the final polyurethane material more durable and excellent;

2. Select the combination of nano-rare earth cerium oxide and polyurethane. Nano-rare earth cerium oxide not only has excellent characteristics such as non-toxicity, stability, etc., but also has good ultraviolet shielding ability, and a small amount of addition will not affect the original color of polyurethane;

3. The chelating type borate coupling agent containing dihydroxy functional group has good hydrolysis resistance due to the chelating group, and can avoid the influence of moisture on the reaction system, which ensures that the preparation method of the present invention has The stability of the polyurethane material with anti-ultraviolet properties.

BEST MODE FOR CARRYING OUT THE INVENTION

A kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 1.0 mol triisopropyl borate and 0.5 g sodium isopropoxide to a three-necked flask with a thermometer, a stirrer, and a reflux condenser, then raise the temperature to 100°C, and add 1.0 mol ethyl alcohol dropwise under constant stirring. Diol, heated to reflux for 100 minutes, then added 1.0 mol of trimethylolpropane, continued the reflux reaction at 150°C for 130 minutes, and distilled off isopropanol under reduced pressure to obtain chelating boric acid containing dihydroxy functional groups Ester coupling agent.

S2. Dry the nano-rare earth cerium oxide at 105°C for 2 hours, and then add it and the chelating borate coupling agent containing dihydroxy functional groups prepared in S1 in a mass ratio of 100:1. React in a high-mixer at 120°C for 30 minutes, and obtain modified nano-rare earth cerium oxide after cooling.

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 4 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Embodiments of the present invention

The present invention is described in further detail below in conjunction with embodiment.

Neither the endpoints nor any values of the ranges disclosed herein are limited to that precise range or value, and these ranges or values are understood to include values close to these ranges. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

Embodiment one: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 0.5 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Embodiment two: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 1.0 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Embodiment three: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 2 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Embodiment four: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 3 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Embodiment five: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

Embodiment six: a kind of polyurethane with anti-ultraviolet performance is prepared according to the following steps:

S3. In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 5 parts of modified nano-rare earth cerium oxide, 0.2 parts of tris(2,4-di-tert-butylphenyl)phosphorous acid Esters, 0.1 part of ethylene bisoleic acid amide were heated, melted and mixed uniformly to obtain the first mixture; the first mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 ° C through metering pumps. Extruding in a granulator, melt blending at 195-200° C., polymerizing in situ, extruding strands, drying and pelletizing to obtain the polyurethane with anti-ultraviolet properties.

Comparative Example 1: In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 0.2 parts of tris(2,4-di-tert-butylphenyl) phosphite, 0.1 part of ethylene bis Oleic acid amide was heated, melted and mixed uniformly to obtain a mixture; the mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to a 100°C twin-screw extrusion granulator through a metering pump, and the mixture was added at 195- Melt blending and in-situ polymerization at 200°C, extrude strands, blow dry, and pelletize to obtain polyurethane.

Comparative Example 2: In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 2 parts of unmodified nano rare earth cerium oxide, 0.2 part of three (2,4-di-tert-butylbenzene base) phosphite, 0.1 part of ethylene bisoleic acid amide heated and melted and mixed uniformly to obtain a mixture; the mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were accurately added to the twin-screw at 100 °C through a metering pump. Extrude into a granulator, melt and blend at 195-200°C, polymerize in situ, extrude strands, blow dry, and pelletize to obtain polyurethane.

Comparative Example 3: In parts by weight, 100 parts of dehydrated polytetrahydrofuran diol (Mn=1200), 2 parts of modified nano-rare earth cerium oxide modified by AEO-9, 0.2 parts of tri(2, 4-di-tert-butylphenyl) phosphite, 0.1 part of ethylene bisoleic acid amide was heated and melted and mixed uniformly to obtain a mixture; the mixture, 80 parts of isocyanate TDI, and 1 part of 1,4-butanediol were passed through a metering pump Accurately add to a twin-screw extruder at 100°C, melt blend at 195-200°C, in-situ polymerize, extrude strands, blow dry, and pelletize to obtain polyurethane.

For the products obtained in Example 1 to Example 6, Comparative Example 1, Comparative Example 2 and Comparative Example 3, the tensile properties were tested before and after 96 hours of ultraviolet light irradiation, and Table 1 was obtained.

Comparing Example 1 to Implementation 6, Comparative Example 2, Comparative Example 3 and Comparative Example 1, it is found that the addition of nanometer rare earth cerium oxide can effectively improve the UV resistance of polyurethane.

Comparing Example 3 with Comparative Example 2, it was found that the nano-rare earth cerium oxide was modified by a self-made chelating borate coupling agent containing dihydroxy functional groups and used as a reactive monomer with other reactive monomers for preparing polyurethane Compared with the polyurethane material obtained by directly blending unmodified nano rare earth cerium oxide with other reactive monomers for preparing polyurethane, the polyurethane material obtained after in-situ polymerization has better anti-ultraviolet effect.

Comparing Example 3 with Comparative Example 3, it was found that the nano-rare earth cerium oxide was modified by a self-made chelating borate coupling agent containing dihydroxy functional groups and used as a reactive monomer with other reactive monomers for preparing polyurethane The polyurethane material obtained after in-situ polymerization has better anti-ultraviolet effect than the polyurethane material obtained by modifying nanometer rare earth cerium oxide with common surfactant.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims

A kind of polyurethane with anti-ultraviolet performance, it is characterized in that, take triisopropyl borate, dihydric alcohol, trihydric alcohol as raw material and add catalyst, control reaction parameter to prepare the chelating type boric acid ester containing dihydroxyl functional group coupling agent, and then use the chelating type borate coupling agent containing dihydroxy functional groups to modify the surface of the nano-rare earth oxide to obtain a modified nano-rare earth oxide, and use the modified nano-rare earth oxide Polymer, polyisocyanate, chain extender, polyester polyol or polyether polyol are used as raw materials to carry out in-situ polymerization to obtain the polyurethane with anti-ultraviolet performance.
A polyurethane with anti-ultraviolet performance according to claim 1, characterized in that, the nano-rare earth oxide is one or both of nano-rare-earth cerium oxide and nano-rare-earth lanthanum oxide.
A kind of polyurethane with anti-ultraviolet performance according to claim 1, it is characterized in that, described catalyst is sodium methylate, sodium ethylate, sodium isopropoxide, sodium tert-butoxide, potassium methylate, potassium ethylate, isopropanol One or both of potassium and potassium tert-butoxide.
A kind of polyurethane with anti-ultraviolet performance according to claim 1, is characterized in that, the molar ratio of described triisopropyl borate, diol, triol is 1:1-1.05:1-1.05.
A kind of polyurethane with anti-ultraviolet performance according to claim 1, is characterized in that, described glycol is the one in ethylene glycol, propylene glycol, butanediol.
A kind of polyurethane with anti-ultraviolet performance according to claim 1, is characterized in that, described trihydric alcohol is a kind of in glycerol, trimethylolpropane.
A kind of polyurethane with anti-ultraviolet performance according to claim 1, it is characterized in that, the mass ratio of described nano-rare earth oxide and the chelating type borate coupling agent containing dihydroxy functional group is 100: 0.1-5.
A kind of preparation method of the polyurethane with anti-ultraviolet property according to claim 1, it is characterized in that, prepare according to the following steps:

S1. In a three-necked flask with a thermometer, a stirrer, and a reflux condenser, add triisopropyl borate and a catalyst, then raise the temperature to 80-130°C, and add glycol dropwise under constant stirring, and heat to reflux for 60- After 120 minutes, add the measured trihydric alcohol, continue the reflux reaction at 130-180°C for 90-150 minutes, and distill the isopropanol under reduced pressure to obtain a chelating borate coupling agent containing dihydroxy functional groups ;

S2. Dry the nano-rare earth oxide at 105°C for 1-4 hours, and then add it to the chelating type borate coupling agent containing dihydroxy functional groups prepared in S1 in proportion and heat it up to 115-140°C React in a high-mixer for 15-60 minutes, and obtain modified nano-rare earth oxides after cooling;

S3. In parts by weight, heat and melt 100 parts of dehydrated polyester polyol or polyether polyol, 0.1-5 parts of modified nano-rare earth oxide, 0.1-1 part of antioxidant, and 0.1-1 part of lubricant Mix uniformly to obtain the first mixture; accurately add the first mixture, 50-150 parts of polyisocyanate, and 0.5-5 parts of chain extender to a twin-screw extrusion granulator at 100°C through a metering pump, and Melt blending and in-situ polymerization at 200° C., extruding strands, drying and pelletizing to obtain the polyurethane with UV resistance.
A kind of preparation method of polyurethane with anti-ultraviolet performance according to claim 8, is characterized in that, described polyester polyol is adipic acid polyester diol, polycarbonate diol, phthalic anhydride polyester diol , polycaprolactone diol, succinic acid polyester diol, glutaric acid polyester diol, azelaic acid polyester diol, dodecanedioic acid polyester diol, 1,4-cyclohexane Dicarboxylic acid polyester diol, dimer acid polyester diol, mixed diacid polyester diol, terephthalic acid polyester diol, polymer polyester diol, isophthalic acid polyester diol, partial One or more of trimellitic acid polyester polyols.
A method for preparing polyurethane with anti-ultraviolet properties according to claim 8, wherein the polyether polyol is polytetrahydrofuran diol, polyoxypropylene diol, tetrahydrofuran-oxypropylene copolyethylene glycol, polyoxypropylene Propylene-oxyethylene diol, polyoxyethylene diol, polytrimethylene ether diol, highly active polyether diol, aniline polyether diol, phenol polyether diol, substituted aniline polyether diol, bisphenol A One or more of /oxyethylene polyether diol, bisphenol A/oxypropylene polyether diol, propylene glycol block polyether.
A kind of preparation method with anti-ultraviolet performance polyurethane according to claim 8, is characterized in that, described polyisocyanate is 4, 4'-Diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate, naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI) ), dimethyl biphenyl diisocyanate (TODI), polyphenyl polymethylene polyisocyanate (PAPI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), xylylene diisocyanate Isocyanate (XDI), tetramethyl-m-xylylene diisocyanate (TMXDI), 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexyl diisocyanate (HTDI), cyclohexane dimethylene One or more of diisocyanate (HXDI), norbornane diisocyanate (NBDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI) .