CN116023626A - Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof - Google Patents
Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of solvent-free polyurethane, in particular to a hydrolysis-resistant high-solid-content closed polyurethane resin composition. The hydrolysis-resistant high-solid closed polyurethane resin composition is mainly prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 6-12 parts of amine curing agent; the closed polyurethane resin is mainly prepared from isocyanate, polyether polyol, polycarbonate polyol, polyether modified castor oil, a chain extender, a sealing agent, a catalyst and a functional auxiliary agent. The method overcomes the problem of solvent pollution during polyurethane synthetic leather production, overcomes the defect of a two-component solvent-free process, and the obtained automobile leather has excellent weather resistance, folding resistance, hydrolysis resistance, wear resistance, mechanical strength and processability, and meets the requirements of the market on new energy automobile leather.
Description
Technical Field
The application relates to the technical field of solvent-free polyurethane, in particular to a hydrolysis-resistant high-solid-content closed polyurethane resin composition and a preparation method thereof.
Background
The traditional polyurethane synthetic leather industry mostly adopts solvent type polyurethane resin sizing agent, and the production process system of the solvent type polyurethane resin sizing agent mainly has two problems: on one hand, the pollution problem is easy to generate in the production process, a large amount of waste liquid and waste gas are generated, and the environment is seriously polluted; on the other hand, there is a residue of solvent in the final finished leather, which adversely affects the safety of the final product. This poses a great threat to the sustainable development of the synthetic leather industry.
The environment-friendly solvent-free resin is generated, the solvent-free synthetic leather process is usually a two-component process, the process has more severe requirements, the resin has low production efficiency when the curing speed is too low, equipment such as a coating head, a scraper and the like is easy to agglomerate when the curing speed is too high, the process belongs to a reaction molding process, the foaming of a solvent-free layer is difficult to control due to water in raw materials, and some bubble-free products cannot be realized.
At present, the performance requirements on the synthetic leather in the fields of new energy automobile leather and the like are high, and the preparation of hydrolysis-resistant high-solid closed polyurethane is urgently needed, so that the problem of solvent pollution during the production of polyurethane synthetic leather is solved, the defect of a two-component solvent-free process is overcome, and the requirements of the market on the new energy automobile leather are met.
Disclosure of Invention
In order to solve the technical problems, the application provides a hydrolysis-resistant high-solid-content closed polyurethane resin composition.
In a first aspect, the present application provides a hydrolysis-resistant high-solid closed polyurethane resin composition, which is realized by the following technical scheme:
the hydrolysis-resistant high-solid closed polyurethane resin composition is mainly prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 6-12 parts of amine curing agent; the closed polyurethane resin is mainly prepared from the following raw materials of isocyanate, polyether polyol, polycarbonate polyol, polyether modified castor oil, a chain extender, a sealing agent, a catalyst, an antioxidant and a functional auxiliary agent;
the average molecular weight of the polycarbonate diol is 1000-3000; the polycarbonate diol is prepared from a mixture of PCL, 1, 6-hexanediol and 3-methylpentanediol or a mixture of PCL, 1, 6-hexanediol and 1, 4-butanediol;
the polyether polyol is at least one of polypropylene oxide dihydric alcohol and polypropylene oxide trihydric alcohol;
the average molecular weight of the polyether polyol is 1000-6000;
The average hydroxyl functionality of the polyether modified castor oil is 3.0, and the hydroxyl value is 56-260 mgKOH/g;
the blocking agent is a mixture of methyl ethyl ketoxime and 3, 5-dimethylpyrazole;
the mass ratio of the methyl ethyl ketoxime to the 3, 5-dimethylpyrazole is 1:9-9:1;
the amine curing agent comprises any one of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane, 4-diamino dicyclohexylmethane and isophorone diamine.
The application overcomes the problem of solvent pollution during polyurethane synthetic leather production, simultaneously makes up the defect of a two-component solvent-free process, and the automobile leather obtained by adopting the hydrolysis-resistant high-solid-content closed polyurethane resin composition has excellent weather resistance, folding resistance, hydrolysis resistance, wear resistance, mechanical strength and processability, and meets the requirements of the market on new energy automobile leather.
Preferably, the closed polyurethane resin is prepared from the following raw materials, by mass, 5-25% of isocyanate, 40-75% of polyether polyol, 5-15% of polycarbon polyol, 5-15% of polyether modified castor oil, 0.5-4% of chain extender, 2-10% of a sealing agent, 0.01-0.2% of a catalyst and the balance of a functional auxiliary agent.
The hydrolysis-resistant high-solid-content sealed polyurethane resin composition is formed by combining sealed polyurethane resin with amine curing agent, isocyanate and hydroxyl components react to generate isocyanate-terminated prepolymer with smaller molecular weight and lower viscosity, the thermally-dissociable sealing agent is utilized to react with the isocyanate-terminated isocyanate to form sealed polyurethane which can be stably stored at room temperature, the amine curing agent is added during use, the amine curing agent has longer storage period at room temperature, the similar operation processability of the traditional single-component resin is realized, the solvent pollution in the traditional synthetic leather production process can be eliminated, meanwhile, the sealing agent is unsealed at high temperature, the amine curing agent reacts rapidly to be cured and formed, the efficiency and the energy conservation are realized, meanwhile, the compact coating without cells is realized, and the leather-like performance is improved.
Preferably, the mass ratio of the methyl ethyl ketoxime to the 3, 5-dimethylpyrazole is 7.8-8: 2 to 2.2.
By adopting the technical scheme, 3,5 dimethylpyrazole has the advantages of low deblocking temperature, high deblocking efficiency and high curing speed, and has the defects that the deblocking speed is too high to facilitate defoaming and leveling in a pre-baking stage, and the solid blocking agent leads to higher resin viscosity and is not easy to process; compared with the solid end-capping agent, the methyl ethyl ketoxime liquid end-capping agent has lower viscosity, slightly higher deblocking temperature and moderate curing speed, is favorable for defoaming and leveling in a pre-baking stage, and has general curing speed, so that the sealing agent obtained by compounding methyl ethyl ketoxime and 3, 5-dimethylpyrazole is provided.
Preferably, the polycarbonate diol is a caprolactone type polycarbonate prepared by taking PCL with an average molecular weight of 2000 as an initiator.
The preferred caprolactone type polycarbonate diol of this application can guarantee that the polyurethane that makes has good weatherability, hydrolysis resistance and wearability, and the viscosity of caprolactone type polycarbonate diol is lower in polycarbonate diol simultaneously, gives this application excellent processability, and cooperates excellent result of use with the polyether polyol that provides in this application.
Preferably, the specific physical and chemical parameters of the polyether modified castor oil are a hydroxyl value of 200gKOH/g, an acid value of 0.5 and a viscosity of 630 mPa.
The polyether modified castor oil used in the application has excellent hydrolysis resistance, can provide certain functionality, and the prepared polyurethane resin has excellent hydrolysis resistance, mechanical strength and good flowability, and improves the overall processing performance.
Preferably, the isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate (MDI-100), a mixture of 2,4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate (MDI-50), toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI).
By adopting the technical scheme, the weather resistance, folding resistance, hydrolysis resistance, wear resistance and mechanical strength of the prepared polyurethane can be ensured.
Preferably, the chain extender is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol and 3-methyl-1, 5-pentanediol;
the catalyst is at least one of an amine catalyst and an organic metal catalyst;
The amine catalyst is at least one of triethanolamine and triethylene diamine;
the organic metal catalyst is at least one of organic tin, organic bismuth, organic potassium and organic zinc.
By adopting the technical scheme, the weather resistance, folding resistance, hydrolysis resistance, wear resistance and mechanical strength of the prepared polyurethane can be ensured.
Preferably, the functional auxiliary agent comprises an antifoaming agent, a leveling agent and a light/heat stabilizer, wherein the antifoaming agent is an organosilicon antifoaming agent, and the organosilicon antifoaming agent is at least one of BYK-060N, BYK-066N, BYK-A530;
the leveling agent is any one of BYK-UV3510, BYK-UV3500, TEGOFlow300, TEGORad2200N and TEGORad 2100;
the light/heat stabilizer is one of ultraviolet absorber and hindered amine light stabilizer;
the ultraviolet absorbent is at least one of UV-1, UV-320, UV-1130, UV-P, UV-1164 and UV-234;
the hindered amine light stabilizer is at least one of light stabilizer 292, light stabilizer 622, light stabilizer 770, light stabilizer 944, light stabilizer 5050, light stabilizer 5060 and light stabilizer 5151;
the antioxidant is at least one of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 and antioxidant 3114.
By adopting the technical scheme, the weather resistance, folding resistance, hydrolysis resistance, wear resistance, mechanical strength and processability of the prepared polyurethane can be ensured.
Preferably, the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine; the triethylenetetramine accounts for 4-8% of the total mass of the amine curing agent.
Through optimizing the composition and the proportion of the amine curing agent, the polyfunctional amine curing agent increases the crosslinking degree, and proper addition can improve the low-temperature curing rate, the stripping force retention rate and the hydrolysis resistance, the prepared product has high strength after curing and can better maintain the stripping force under the conditions of high temperature and high humidity.
In a second aspect, the preparation method of the hydrolysis-resistant high-solid-content closed polyurethane resin composition provided by the application is realized by the following technical scheme:
a preparation method of hydrolysis-resistant high-solid-content closed polyurethane resin composition comprises the following steps:
s1, adding isocyanate and an antioxidant at 20-40 ℃ and stirring for 8-12min;
s2, sequentially adding polyether polyol, polycarbon polyol and polyether modified castor oil, and then reacting for 1-2h at 70-80 ℃;
S3, adding a chain extender, and reacting at 70-80 ℃ until the NCO mass content in the system reaches 2-4%, thereby obtaining an isocyanate-terminated prepolymer;
s4, adding a sealing agent and a catalyst to carry out end-capping reaction, and reacting at 70-80 ℃ until the NCO mass content in the system is 0%;
s5, adding functional auxiliary agents, stirring for 20-35min, and cooling to room temperature to obtain closed high-solid resin;
s6, uniformly mixing the closed high-solid resin and the amine curing agent according to a proportion to obtain the hydrolysis-resistant high-solid closed polyurethane resin composition
The preparation method is relatively simple, is convenient for industrialized mass production, and is clean and environment-friendly, and compared with the traditional solvent type resin process, the preparation method provided by the application has no pollution problem of any solvent. After the amine curing agent is added into the closed high-solid resin prepared by the method, the storage period of more than 24 hours can be achieved at room temperature, an original solvent type production line can be adopted, special equipment for solvent-free synthetic leather is not needed to be additionally arranged, and the cost of converting and developing the traditional synthetic leather enterprises into environment-friendly synthetic leather is reduced.
In summary, the present application has the following advantages:
1. the method overcomes the problem of solvent pollution during polyurethane synthetic leather production, overcomes the defect of a two-component solvent-free process, and the obtained automobile leather has excellent weather resistance, folding resistance, hydrolysis resistance, wear resistance, mechanical strength and processability, and meets the requirements of the market on new energy automobile leather.
2. The preparation method is relatively simple and is convenient for industrialized mass production.
3. Compared with the traditional solvent type resin process, the preparation method provided by the application has no pollution problem of any solvent, and is clean and environment-friendly.
4. After the amine curing agent is added into the closed high-solid resin prepared by the method, the storage period of more than 24 hours can be achieved at room temperature, an original solvent type production line can be adopted, special equipment for solvent-free synthetic leather is not needed to be additionally arranged, and the cost of converting and developing the traditional synthetic leather enterprises into environment-friendly synthetic leather is reduced.
5. The hydrolysis-resistant high-solid-content closed polyurethane resin prepared by the invention has the characteristics of high solid content, low viscosity and excellent processability, and the prepared leather sample has excellent physical properties, the retention rate of peel strength of the leather sample at 70 ℃ under the conditions of 95% humidity and constant temperature and humidity for 10 weeks can reach more than 80%, the normal-temperature folding resistance is more than 10 ten thousand times, and the folding resistance at-15 ℃ is more than 5 ten thousand times.
Detailed Description
Examples
Example 1
The hydrolysis-resistant high-solid-content closed polyurethane resin composition disclosed by the application is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 6 parts of amine curing agent. In this example, 3-dimethyl-4, 4-diaminodicyclohexylmethane was used as the amine curing agent.
The blocked polyurethane resin was prepared from 375.25g of 4,4' -diphenylmethane diisocyanate MDI-100 (Wanhua chemical Co., ltd.), 1132g of polypropylene oxide glycol having an average molecular weight of 3000 (Cokia polyol (Nanjing Co., ltd.), 252g of caprolactone type polycarbonate glycol having an average molecular weight of 2000 (Japanese Kogyo Co., ltd.), 127.68g of polyether-modified castor oil (Eyew oil Co., ltd., hydroxyl value of 200, acid value of 0.5, viscosity/mPa.s 630, functionality of 3), 12.54g of ethylene glycol, 86.81g of methyl ethyl ketoxime, 23.95g of 3,5 dimethylpyrazole, 0.24g of catalyst-bismuth octopamoate, 2.41g of antifoaming agent BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.41g of ultraviolet absorber UV-P, and 2.3g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 8:2.
A preparation method of hydrolysis-resistant high-solid-content closed polyurethane resin composition comprises the following steps: s1, adding 375.25g of MDI-100 into a medium-three-neck flask, heating to 30 ℃, adding 2.3g of antioxidant 1010, and stirring for 10min for later use;
s2, sequentially adding 1257g of polypropylene oxide dihydric alcohol with average molecular weight of 3000, 252g of caprolactone type polycarbonate dihydric alcohol with average molecular weight of 2000 and 127.68g of polyether modified castor oil, uniformly stirring, and heating to 70 ℃ for reaction for 1h;
S3, adding 12.54g of ethylene glycol, and reacting at 70 ℃ for 1.5 hours until the NCO mass fraction content reaches 2.5%, so as to obtain an isocyanate-terminated prepolymer for later use;
s4, adding 86.81g of methyl ethyl ketoxime, 23.95g of 3, 5-dimethylpyrazole and 0.23g of bismuth octoate for end-capping reaction, and reacting at 80 ℃ for 1.5 hours until the NCO mass content in the system is 0%;
s5, adding 2.3g of defoaming agent BYK-060N, 6.7g of flatting agent BYK-UV3510, 2.3g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010, stirring for 30min, and cooling to room temperature to obtain closed high-solid resin;
s6, uniformly mixing the closed high-solid resin and the amine curing agent according to the weight ratio of 100:6 to obtain the hydrolysis-resistant high-solid closed polyurethane resin composition.
The hydrolysis-resistant high-solid closed polyurethane resin composition is applied to the preparation of automobile leather: mixing the hydrolysis-resistant high-solid sealing polyurethane resin composition, smearing the mixture on a polyurethane surface layer, preheating the mixture at 90-120 ℃ for 1-2min for leveling and defoaming, placing the mixture in a baking oven at 130-150 ℃ for curing reaction for 1-5min, completely curing the mixture, directly coating a backing material, attaching base cloth for drying, and stripping to obtain the hydrolysis-resistant synthetic leather.
Example 2
Example 2 differs from example 1 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 8 parts of amine curing agent.
Example 3
Example 3 differs from example 1 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 9 parts of amine curing agent.
Example 4
Example 4 differs from example 1 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 10 parts of amine curing agent.
Example 5
Example 5 differs from example 1 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 12 parts of amine curing agent.
Example 6
Example 6 differs from example 1 in that:
the blocked polyurethane resin was prepared from 375.25g of MDI-100, 1132g of polypropylene oxide diol with an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol with an average molecular weight of 2000, 127.68g of polyether-modified castor oil, 12.54g of ethylene glycol, 10.85g of methyl ethyl ketoxime, 107.75g of 3, 5-dimethylpyrazole, 0.24g of catalyst-bismuth octopaminate, 2.42g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 1:9.
Example 7
Example 7 differs from example 1 in that:
the blocked polyurethane resin was prepared from 375.25g of MDI-100, 1132g of polypropylene oxide diol with an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol with an average molecular weight of 2000, 127.68g of polyether-modified castor oil, 12.54g of ethylene glycol, 97.66g of methyl ethyl ketoxime, 11.97g of 3, 5-dimethylpyrazole, 0.24g of bismuth octopamate as a catalyst, 2.42g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 9:1.
Example 8
Example 8 differs from example 1 in that:
the blocked polyurethane resin was prepared from 375.25g of MDI-100, 1132g of polypropylene oxide diol with an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol with an average molecular weight of 2000, 127.68g of polyether-modified castor oil, 12.54g of ethylene glycol, 43.4g of methyl ethyl ketoxime, 71.83g of 3, 5-dimethylpyrazole, 0.24g of bismuth octopamate as a catalyst, 2.42g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 4:6.
Example 9
Example 9 differs from example 1 in that:
the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 8.5 parts of amine curing agent.
The blocked polyurethane resin was prepared from 211.75g of TDI (Wanhua chemical Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000 (Coptis polyol (Nanjing) Co., ltd.), 148.50g of a caprolactone-type polycarbonate glycol having an average molecular weight of 2000 (Cellonite, japan Co., ltd.), 129.97g of polyether-modified castor oil (Eyew oil Co., ltd.), 18.57g of 1, 4-butanediol, 77.47g of methyl ethyl ketoxime, 21.37g of 3,5 dimethylpyrazole, 0.22g of catalyst-octornide bismuth, 2.16g of an antifoaming agent BYK-A530, 6.29g of BYK-UV3500, 2.16g of an ultraviolet light absorber UV-1, and 2.30g of an antioxidant 245.
Example 10
Example 10 differs from example 9 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 6 parts of amine curing agent.
Example 11
Example 11 differs from example 9 in that: the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 12 parts of amine curing agent.
Example 12
Example 12 differs from example 9 in that:
the blocked polyurethane resin was prepared from 211.72g of TDI (Wanhua chemical group Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000, 148.50g of caprolactam type polycarbonate glycol having an average molecular weight of 2000, 129.97g of polyether-modified castor oil, 18.57g of 1, 4-butanediol, 9.68g of methyl ethyl ketoxime, 91.13g of 3,5 dimethylpyrazole, 0.22g of bismuth octoate as a catalyst, 2.16g of defoaming agent BYK-A530, 6.31g of leveling agent BYK-UV3500, 2.16g of ultraviolet light absorber UV-1, and 2.30g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 1:9.
Example 13
Example 13 differs from example 9 in that:
the blocked polyurethane resin was prepared from 211.72g of TDI (Wanhua chemical group Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000, 148.50g of caprolactam type polycarbonate glycol having an average molecular weight of 2000, 129.97g of polyether-modified castor oil, 18.57g of 1, 4-butanediol, 87.17g of methyl ethyl ketoxime, 10.69g of 3, 5-dimethylpyrazole, 0.22g of bismuth octoate as a catalyst, 2.16g of defoaming agent BYK-A530, 6.31g of leveling agent BYK-UV3500, 2.16g of ultraviolet light absorber UV-1, and 2.30g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 9:1.
Example 14
Example 14 differs from example 9 in that:
the blocked polyurethane resin was prepared from 211.72g of TDI (Wanhua chemical group Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000, 148.50g of caprolactam type polycarbonate glycol having an average molecular weight of 2000, 129.97g of polyether-modified castor oil, 18.57g of 1, 4-butanediol, 38.74g of methyl ethyl ketoxime, 64.12g of 3,5 dimethylpyrazole, 0.22g of bismuth octoate as a catalyst, 2.16g of defoaming agent BYK-A530, 6.31g of leveling agent BYK-UV3500, 2.16g of ultraviolet light absorber UV-1, and 2.30g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 4:6.
Example 15
Example 15 differs from example 1 in that:
the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 10.5 parts of amine curing agent.
The blocked polyurethane resin was prepared from 325.6g of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 980.65g of polypropylene oxide glycol having an average molecular weight of 4000 (Coptis polyol (Nanjing)) 89.15g of a caprolactone type polycarbonate glycol having an average molecular weight of 1000, 178.3g of polyether modified castor oil, 8.92g of 1, 4-butanediol, 72.26g of methyl ethyl ketoxime, 19.93g of 3,5 dimethylpyrazole, 0.20g of bismuth octoate as a catalyst, 2.01g of an antifoaming agent BYK-A530, 5.86g of a leveling agent TEGORad2100, 2.01g of an ultraviolet light absorber UV-1, and 2.30g of an antioxidant 1035.
Example 16
Example 16 differs from example 1 in that: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine (Henschel polyurethane (China Co.). Wherein triethylenetetramine accounts for 4% of the total mass of the amine curing agent.
Example 17
Example 17 differs from example 1 in that: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine. Wherein triethylenetetramine accounts for 6% of the total mass of the amine curing agent.
Example 18
Example 18 differs from example 1 in that: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine. Wherein triethylenetetramine accounts for 8% of the total mass of the amine curing agent.
Example 19
Example 19 differs from example 1 in that: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine. Wherein triethylenetetramine accounts for 2% of the total mass of the amine curing agent.
Example 20
Example 20 differs from example 1 in that: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine. Wherein triethylenetetramine accounts for 10% of the total mass of the amine curing agent.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that:
the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 5 parts of amine curing agent.
Comparative example 2
Comparative example 2 differs from example 1 in that:
the hydrolysis-resistant high-solid closed polyurethane resin composition is prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 13 parts of amine curing agent.
Comparative example 3
Comparative example 3 differs from example 1 in that:
the closed polyurethane resin is prepared from 375.25g of MDI-100, 1132g of polypropylene oxide dihydric alcohol with average molecular weight of 3000, 252g of caprolactone type polycarbonate dihydric alcohol with average molecular weight of 2000, 127.68g of polyether modified castor oil, 12.54g of ethylene glycol, 108.51g of methyl ethyl ketoxime, 0.24g of catalyst-bismuth octo-canthaxanthin, 2.42g of defoamer BYK-060N, 6.68g of flatting agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010.
Comparative example 4
Comparative example 4 differs from example 1 in that:
the closed polyurethane resin is prepared from 375.25g of MDI-100, 1132g of polypropylene oxide dihydric alcohol with average molecular weight of 3000, 252g of caprolactone type polycarbonate dihydric alcohol with average molecular weight of 2000, 127.68g of polyether modified castor oil, 12.54g of ethylene glycol, 119.73g of 3,5 dimethylpyrazole, 0.24g of catalyst-bismuth octopamoate, 2.42g of defoamer BYK-060N, 6.68g of flatting agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010.
Comparative example 5
Comparative example 5 differs from example 1 in that:
the blocked polyurethane resin was prepared from 375.25g of MDI-100, 1132g of polypropylene oxide diol with an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol with an average molecular weight of 2000, 127.68g of polyether-modified castor oil, 12.54g of ethylene glycol, 5.43g of methyl ethyl ketoxime, 113.84g of 3, 5-dimethylpyrazole, 0.24g of catalyst-bismuth octopaminate, 2.42g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3,5 dimethyl pyrazole is 0.5:9.5.
Comparative example 6
Comparative example 6 differs from example 1 in that:
the blocked polyurethane resin was prepared from 375.25g of MDI-100, 1132g of polypropylene oxide diol with an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol with an average molecular weight of 2000, 127.68g of polyether-modified castor oil, 12.54g of ethylene glycol, 103.08g of methyl ethyl ketoxime, 5.99g of 3, 5-dimethylpyrazole, 0.24g of catalyst-bismuth octopamate, 2.42g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.42g of ultraviolet light absorber UV-P and 2.3g of antioxidant 1010.
Comparative example 7
Comparative example 7 differs from example 1 in that:
the blocked polyurethane resin is prepared by replacing polypropylene oxide dihydric alcohol with average molecular weight of 3000 with PTMEG polyether glycol with average molecular weight of 3000.
Comparative example 8
Comparative example 8 differs from example 1 in that:
the blocked polyurethane resin is prepared by replacing a caprolactone type polycarbonate diol with average molecular weight of 2000 with a polycarbonate diol with average molecular weight of 2000 (CAS number: 29862-10-0).
Comparative example 9
Comparative example 9 differs from example 1 in that:
the blocked polyurethane resin was prepared from 328.85g of MDI-100, 1259.68g of polypropylene oxide diol having an average molecular weight of 3000, 252g of caprolactone-type polycarbonate diol having an average molecular weight of 2000, 12.54g of ethylene glycol, 86.81g of methyl ethyl ketoxime, 23.95g of 3,5 dimethylpyrazole, 0.4g of catalyst-bismuth octopamoate, 2.36g of defoamer BYK-060N, 6.68g of leveling agent BYK-UV3510, 2.36g of ultraviolet light absorber UV-P, and 2.3g of antioxidant 1010.
Comparative example 10
Comparative example 10 example 9 differs in:
the blocked polyurethane resin was prepared from 211.72g of TDI (Wanhua chemical Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000 (Coptis polyol (Nanjing) Co., ltd.), 148.5g of a caprolactone-type polycarbonate glycol having an average molecular weight of 2000 (Japanese Kogyo Co., ltd.), 129.97g of polyether-modified castor oil (Eyew oil Co., ltd.), 18.57g of 1, 4-butanediol, 4.84g of methyl ethyl ketoxime, 101.47g of 3, 5-dimethylpyrazole, 0.20g of catalyst-bismuth octo-zornide, 3.24g of defoamer BYK-A530, 5.5g of leveling agent BYK-UV3500, 2.18g of ultraviolet light absorber UV-1, and 2.18g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 0.05:0.95.
Comparative example 11
Comparative example 11 example 9 differs in:
the blocked polyurethane resin was prepared from 211.72g of TDI (Wanhua chemical Co., ltd.), 1188.32g of polypropylene oxide glycol having an average molecular weight of 6000 (Coptis polyol (Nanjing) Co., ltd.), 148.5g of a caprolactone-type polycarbonate glycol having an average molecular weight of 2000 (Japanese Kogyo Co., ltd.), 129.97g of polyether-modified castor oil (Eyew oil Co., ltd.), 18.57g of 1, 4-butanediol, 91.96g of methyl ethyl ketoxime, 5.34g of 3, 5-dimethylpyrazole, 0.20g of catalyst-bismuth octo-zornide, 3.24g of defoamer BYK-A530, 5.5g of leveling agent BYK-UV3500, 2.18g of ultraviolet absorber UV-1, and 2.18g of antioxidant 1010. Wherein, the mol ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 0.95:0.05.
Performance test
Detection method/test method
Preparation of automobile leather: the hydrolysis-resistant high-solid-content polyurethane resin compositions prepared in examples 1 to 20 and comparative examples 1 to 11 were knife-coated on HX-6120 (hydrolysis-resistant polyurethane topcoat resin produced by Zhejiang Hexin technology Co., ltd.), preheated at 110℃for 1 minute, reacted in an oven at 130℃for 5 minutes to be completely cured, then coated with a primer HX-GD45 (high-solid primer produced by Zhejiang Hexin technology Co., ltd.), attached to a base cloth, baked and peeled off to obtain a synthetic leather product.
1. Peel strength: according to QB/T2888-2007 standard test.
2. Hydrolysis resistance test: after 10 weeks of jungle testing in a constant temperature and humidity cabinet at 70 ℃ and 95% rh, the peel strength was tested according to QB/T2888-2007 standard.
3. weather-light-JungleTest: after the test sample and the comparison sample are respectively placed in an environment with 80 ℃ and 75% humidity for 400 hours, the test sample and the comparison sample are bent for 10 ten thousand times at 25 ℃ to observe whether the test sample is cracked or not; bending at-15deg.C for 5 ten thousand times to see if cracking.
4. Mechanical strength test of resin coating: the hydrolysis-resistant high-solid-content blocked polyurethane resin compositions prepared in examples 1 to 20 and comparative examples 1 to 11 were cured at 130℃to give sample films 1 to 10 and comparative films 1 to 9, and the elongation and break strength were measured and tested in accordance with GB/T1040.3-2006.
1. Purpose of testing
The maximum load that a specimen of a predetermined size can withstand when it is broken by an external force and the elongation of the specimen at that time are detected.
2. Apparatus and device
Electronic tension machine (speed: 0-500mm/min, maximum load: 500N/5000N, precision: 1N), sheet punching machine, standard cutter (rectangular), thickness gauge: precision of 0.001mm
Parameters of the tensile machine are as follows:
1. Stretching speed: 100mm/min;
2. sample width: 20.0mm;
3. initial distance of clamp: 50.0mm.
3. The operation steps are as follows:
1. the required samples are cut by a standard cutter, each group of samples is not less than three, all the samples are required to have no bubbles, no cracks, no pinholes, no gaps and smooth edges within 50mm of the marked line.
2. Thickness measurement was carried out according to GB/T1040.3-2006, the same sample being marked with a thickness value within 50.0mm
0.03mm, deviation less than 0.01mm, otherwise, the method is disabled.
2. Inputting the thickness value of the sample, clamping the sample in an upper clamp and a lower clamp of an electronic tension machine, confirming the stretching speed to be 100mm/min, selecting the test state as 'film stretching', and starting the tension machine.
3. When the sample breaks, the pulling machine automatically resets. At this time, data on 100% modulus, breaking strength, elongation at break, and the like are recorded.
4. Test results: at least two test results are averaged to obtain a final result (when the 100% modulus value is 9.0MPa or more, the deviation should be less than 2.0MPa, when the 100% modulus value is less than 9.0MPa, the deviation should be less than 1.0MPa, the average relative deviation of fracture strength is not more than 10%, the average relative deviation of fracture elongation is not more than 25%, otherwise, the deviation is eliminated).
4. Testing related data
Tensile strength (MPa): maximum force (N)/cross-sectional area;
elongation at break: (length at stretch-break-original length)/original length 50mm;
100% stress: force/cross-sectional area at 100% displacement.
5. Light fastness test: xenon lamp testing was performed in accordance with ISO 105-B06.
6. Vulcanization resistance test: tested according to GMW 14864-2012.
Data analysis
Table 1 shows the detection parameters of examples 1 to 20 and comparative examples 1 to 11
Table 2 shows the detection parameters of examples 1 to 20 and comparative examples 1 to 11
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the combination of table 1, examples 1 to 5 and comparative examples 1 to 2, the prepared automotive leather in examples 1 to 5 has a 10-week peel strength retention of 80 to 90% under conditions of constant temperature and humidity at 70 ℃ and 95%, while the comparative examples 1 to 2 has a 10-week peel strength retention of about 60 to 72%; as can be seen from Table 2, the mechanical properties of comparative examples 1-2 are significantly reduced compared with those of examples 1-5, and the vulcanization and light resistance of examples 1-5 are better than those of comparative example 1, and are not much different from those of comparative example 2, so that the use amount of amine curing agent is controlled to be 6-12 parts under the condition that 100 parts of closed polyurethane resin is selected, the addition amount of amine curing agent is controlled to be 6-12 parts, the addition amount is less than 6 parts, the physical properties of the product are poor, the stripping force is low, the addition amount is more than 12 parts, and the stripping force of the product is seriously attenuated under high temperature and high humidity.
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the combination of Table 1, the mechanical properties and 10-week peel strength retention of examples 2 to 4 are superior to those of examples 1 and 5, and therefore, the use amount of the amine curing agent is controlled to 8 to 10 parts by selecting 100 parts of the blocked polyurethane resin, and the low-temperature curing rate, the peel force retention and the hydrolysis resistance are further improved.
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the comparison of Table 1, examples 1 and 6 to 8 and comparative examples 3 to 6, the retention of 10-week peel strength of examples 1, 6 to 8 can reach 85 to 90%, the retention of 10-week peel strength of comparative examples 3 to 6 is better than that of comparative examples 1, 6 to 8, and the folding endurance of examples 1, 6 to 8 is better than that of comparative examples 4, and the difference between comparative examples 3 and 5 to 6 is not great, but the mechanical strength of examples 1, 6 to 8 is better than that of comparative examples 3 to 6, in combination with Table 2, therefore, the sealant is a mixture of methyl ethyl ketoxime and 3, 5-dimethylpyrazole, the mass ratio of methyl ketoxime and 3, 5-dimethylpyrazole is 1:9 to 9:1, and the prepared automobile has good weather resistance, hydrolysis resistance, and 10-week peel strength retention under conditions of constant temperature and humidity of 70 ℃ and 95% can reach 85 to 90%. Preferably, the mass ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 8:2.
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the combination of Table 1, the 10-week peel strength retention of examples 9 and 12 to 14 is better than that of comparative examples 10 to 11, and the mechanical properties of examples 9 and 12 to 14 are better than that of comparative examples 10 to 11, and the combination of Table 2 shows that the sealant is a mixture of methyl ethyl ketoxime and 3, 5-dimethylpyrazole, and the mass ratio of methyl ethyl ketoxime and 3, 5-dimethylpyrazole is 1:9 to 9:1, so that the resin film has good mechanical strength, vulcanization resistance and light resistance, and the prepared automobile has good weather resistance and hydrolysis resistance. Preferably, the mass ratio of methyl ethyl ketoxime to 3, 5-dimethylpyrazole is 8:2.
As can be seen from the combination of examples 1-20 and comparative examples 1-11 and the combination of Table 1, the 10-week peel strength retention of examples 16-18 is slightly better than that of examples 1, 19-20, and the mechanical strength of examples 16-18 is better than that of examples 1, 19-20, as can be seen from the combination of Table 2, the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane and triethylenetetramine, and the resin film is endowed with good mechanical strength, vulcanization resistance and light resistance, and the prepared automobile has good weather resistance and hydrolysis resistance. Preferably, triethylenetetramine accounts for 4-8% of the total mass of the amine curing agent, and the polyfunctional amine curing agent increases the crosslinking degree, and the physical properties and hydrolysis resistance can be improved by proper addition.
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the combination of tables 1 to 2, the peel strength of example 1 and the peel strength of example 1 after 10 weeks of jungle test are slightly better than those of comparative example 7, but the difference is smaller, and the folding endurance of example 1 is similar to that of comparative example 7; as can be seen from Table 2, the tensile breaking rate and breaking strength of example 1 are slightly better than those of comparative example 7, but the difference between them is smaller, but the viscosity of the resin of comparative example 7 is larger, so that the hydrolysis-resistant high-solid-content enclosed polyurethane resin composition prepared from caprolactone type polycarbonate and polyether modified castor oil, which are prepared from PCL with average molecular weight of 3000-6000 and PCL with average molecular weight of 1000-2000, is low in viscosity and better in processability, and can endow the resin film with good mechanical strength, vulcanization resistance and light resistance, and the prepared automobile has good weather resistance and hydrolysis resistance.
As can be seen from the combination of examples 1 to 20 and comparative examples 1 to 11 and the combination of tables 1 to 2, the peel strength of example 1 was slightly greater than that of comparative example 8, the peel strength of example 1 after 10 weeks of jungle test was greater than that of comparative example 8, and the bending at 25 c of example 1 was 10 ten thousand times, -15 c was 5 ten thousand times without cracking, and the bending at-15 c of comparative example 8 was 5 ten thousand times without cracking; as can be seen from Table 2, the tensile fracture rate of example 1 is slightly larger than that of comparative example 8, the fracture strength of example 1 is larger than that of comparative example 8, and the vulcanization resistance and light resistance of example 1 are better, so that the hydrolysis-resistant high-solid-content enclosed polyurethane resin composition prepared from caprolactone type polycarbonate and polyether modified castor oil prepared from PCL with average molecular weight of 3000-6000 and PCL with average molecular weight of 1000-2000 serving as starting agents is endowed with good mechanical strength, vulcanization resistance and light resistance to the resin film, and the prepared automobile has good weather resistance, hydrolysis resistance and better low-temperature flexibility.
As can be seen from the combination of examples 1-20 and comparative examples 1-11 and the combination of tables 1-2, the peel strength of example 1 is slightly greater than that of comparative example 9, and the peel strength of example 1 after 10 weeks of jungle test is greater than that of comparative example 9, both of which are similar in folding endurance; as can be seen from Table 2, the tensile breaking rate of example 1 is slightly larger than that of comparative example 9, the breaking strength of example 1 is larger than that of comparative example 9, and the vulcanization resistance effect of example 1 is better, so that the hydrolysis-resistant high-solid-content enclosed polyurethane resin composition prepared from caprolactone type polycarbonate and polyether modified castor oil, which are prepared from PCL with average molecular weight of 3000-6000 and PCL with average molecular weight of 1000-2000, is used as an initiator, and the prepared automobile has good mechanical strength, vulcanization resistance and light resistance.
In summary, the present application has the following advantages:
1. the method overcomes the problem of solvent pollution during polyurethane synthetic leather production, overcomes the defect of a two-component solvent-free process, and the obtained automobile leather has excellent weather resistance, folding resistance, hydrolysis resistance, wear resistance, mechanical strength and processability, and meets the requirements of the market on new energy automobile leather.
2. The preparation method is relatively simple, is convenient for industrialized mass production, and is clean and environment-friendly, and compared with the traditional solvent type resin process, the preparation method provided by the application has no pollution problem of any solvent.
3. After the amine curing agent is added into the closed high-solid resin prepared by the method, the storage period of more than 24 hours can be achieved at room temperature, an original solvent type production line can be adopted, special equipment for solvent-free synthetic leather is not needed to be additionally arranged, and the cost of converting and developing the traditional synthetic leather enterprises into environment-friendly synthetic leather is reduced.
4. The hydrolysis-resistant high-solid-content closed polyurethane resin prepared by the invention has the characteristics of high solid content, low viscosity and excellent processability, and the prepared leather sample has excellent physical properties, the retention rate of peel strength of the leather sample at 70 ℃ under the conditions of 95% humidity and constant temperature and humidity for 10 weeks can reach more than 80%, the normal-temperature folding resistance is more than 10 ten thousand times, and the folding resistance at-15 ℃ is more than 5 ten thousand times.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. A hydrolysis-resistant high-solid-content closed polyurethane resin composition is characterized in that: the material is mainly prepared from the following raw materials in parts by weight: 100 parts of closed polyurethane resin and 6-12 parts of amine curing agent; the closed polyurethane resin is mainly prepared from the following raw materials of isocyanate, polyether polyol, polycarbonate polyol, polyether modified castor oil, a chain extender, a sealing agent, a catalyst, an antioxidant and a functional auxiliary agent;
the average molecular weight of the polycarbonate diol is 1000-3000; the polycarbonate diol is prepared from a mixture of PCL, 1, 6-hexanediol and 3-methylpentanediol or a mixture of PCL, 1, 6-hexanediol and 1, 4-butanediol;
the polyether polyol is at least one of polypropylene oxide dihydric alcohol and polypropylene oxide trihydric alcohol;
the average molecular weight of the polyether polyol is 1000-6000;
the average hydroxyl functionality of the polyether modified castor oil is 3.0, and the hydroxyl value is 56-260 mgKOH/g;
the blocking agent is a mixture of methyl ethyl ketoxime and 3, 5-dimethylpyrazole;
the molar ratio of the methyl ethyl ketoxime to the 3, 5-dimethylpyrazole is 1:9-9:1;
the amine curing agent comprises any one of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane, 4-diamino dicyclohexylmethane and triethylenetetramine.
2. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the closed polyurethane resin is prepared from the following raw materials, by mass, 5-25% of isocyanate, 40-75% of polyether polyol, 5-15% of polycarbon polyol, 5-15% of polyether modified castor oil, 0.5-4% of chain extender, 2-10% of sealing agent, 0.01-0.2% of catalyst and the balance of functional auxiliary agent.
3. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the molar ratio of the methyl ethyl ketoxime to the 3, 5-dimethylpyrazole is 7.8-8: 2 to 2.2.
4. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the polycarbonate diol is caprolactone type polycarbonate prepared by taking PCL with an average molecular weight of 2000 as an initiator.
5. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the specific physical and chemical parameters of the polyether modified castor oil are that the hydroxyl value is 200gKOH/g, the acid value is 0.5, and the viscosity is 630 mPa.
6. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate (MDI-100), a mixture of 2,4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate (MDI-50), toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI).
7. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the chain extender is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol and 3-methyl-1, 5-pentanediol;
the catalyst is at least one of an amine catalyst and an organic metal catalyst;
the amine catalyst is at least one of triethanolamine and triethylene diamine;
the organic metal catalyst is at least one of organic tin, organic bismuth, organic potassium and organic zinc.
8. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the functional auxiliary agent comprises a defoaming agent, a leveling agent and a light/heat stabilizer, wherein the defoaming agent is an organosilicon defoaming agent, and the organosilicon defoaming agent is at least one of BYK-060N, BYK-066N, BYK-A530;
the leveling agent is any one of BYK-UV3510, BYK-UV3500, TEGOFlow300, TEGORad2200N and TEGORad 2100;
the light/heat stabilizer is one of ultraviolet absorber and hindered amine light stabilizer;
the ultraviolet absorbent is at least one of UV-1, UV-320, UV-1130, UV-P, UV-1164 and UV-234;
The hindered amine light stabilizer is at least one of light stabilizer 292, light stabilizer 622, light stabilizer 770, light stabilizer 944, light stabilizer 5050, light stabilizer 5060 and light stabilizer 5151;
the antioxidant is at least one of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 and antioxidant 3114.
9. The hydrolysis-resistant high-solid-content blocked polyurethane resin composition according to claim 1, wherein: the amine curing agent is a mixture of 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane and triethylenetetramine; the triethylenetetramine accounts for 4-8% of the total mass of the amine curing agent.
10. The process for producing a hydrolysis-resistant high-solids blocked polyurethane resin composition as claimed in any one of claims 1 to 9, characterized in that: the method comprises the following steps:
s1, adding isocyanate and an antioxidant at 20-40 ℃ and stirring for 8-12min;
s2, sequentially adding polyether polyol, polycarbon polyol and polyether modified castor oil, and then reacting for 1-2h at 70-80 ℃;
s3, adding a chain extender, and reacting at 70-80 ℃ until the NCO mass content in the system reaches 2-4%, thereby obtaining an isocyanate-terminated prepolymer;
S4, adding a sealing agent and a catalyst to carry out end-capping reaction, and reacting at 70-80 ℃ until the NCO mass content in the system is 0%;
s5, adding functional auxiliary agents, stirring for 20-35min, and cooling to room temperature to obtain closed high-solid resin;
s6, uniformly mixing the closed high-solid resin and the amine curing agent according to a proportion to obtain the hydrolysis-resistant high-solid closed polyurethane resin composition.
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| CN116444759B (en) * | 2023-06-13 | 2023-10-03 | 旭川化学（苏州）有限公司 | Solvent-free polyurethane resin composition and application thereof |
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