CN112480356A - Arylamine modified wet-process polyurethane resin for space leather and preparation method thereof - Google Patents
Arylamine modified wet-process polyurethane resin for space leather and preparation method thereof Download PDFInfo
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- CN112480356A CN112480356A CN202011404820.9A CN202011404820A CN112480356A CN 112480356 A CN112480356 A CN 112480356A CN 202011404820 A CN202011404820 A CN 202011404820A CN 112480356 A CN112480356 A CN 112480356A
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- polyurethane resin
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- isocyanate
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
Abstract
The invention discloses an arylamine modified wet polyurethane resin for space leather and a preparation method thereof. Therefore, the formed molecular chain crystallization micro-area structure is smaller and more regular, and the physical property and the strength shown after the leather is made are higher, and the weather resistance and the hydrolysis resistance stability are better.
Description
Technical Field
The invention relates to the technical field of polyurethane synthetic leather, and particularly relates to arylamine modified wet polyurethane resin for space leather and a preparation method thereof.
Background
Wet polyurethane synthetic leather is the best substitute product of a new generation of natural leather, and has excellent performances, such as good air permeability, moisture permeability, smooth and plump hand feeling and excellent mechanical strength, and is similar to natural leather in structure, so that the product is widely applied to the fields of clothing, shoes, bags, automobile cushions, sofas and the like.
Among them, the high-stripping wet-process polyurethane synthetic leather is well received by the market of sports shoes, and gradually replaces genuine leather to process the sports shoes. Sports shoes are more severe than business and casual shoes in service environment, are more easily corroded by sweat, rainwater and the like when being worn, and need to keep better strength and impact resistance under such severe environment, so that the synthetic leather is required to have high original strength and good alkali resistance, weather resistance and hydrolysis resistance.
Disclosure of Invention
The invention provides a wet polyurethane resin for arylamine modified space leather and a preparation method thereof, aiming at solving the problems of hydrolysis phenomenon, molecular chain breakage, strength reduction of leather products, impact resistance reduction, surface cracking of the leather products and the like caused by ester groups (-COO-) and other groups in a chain segment structure of wet high-stripping polyurethane in the using process. The molecular chain of the wet-process polyurethane resin has higher strength and better weather resistance, hydrolysis resistance and stability.
The invention relates to arylamine modified wet polyurethane resin for space leather, which comprises the following raw materials in percentage by weight:
isocyanate, the amount of which accounts for 5-10% of the total mass of the system;
the polyol compound accounts for 15-25% of the total weight of the system;
the dosage of the binary arylamine compound accounts for 0-3% of the total mass of the system;
the using amount of the dihydric alcohol chain extender accounts for 1 to 3 percent of the total mass of the system;
the catalyst is organic tin catalyst or organic bismuth catalyst, and the amount of the catalyst is 0.001-0.05% of the mass of the polyalcohol compound;
the adding amount of the negative catalyst phosphoric acid is 0 to 0.001 percent of the total mass of the system;
the addition amount of methanol as a reaction terminator is 0.005-0.015 percent of the total mass of the system;
the auxiliary agent is one or more of surfactant, antioxidant, ultraviolet absorbent, weather-resistant stabilizer, waterproof decomposer and anti-sticking agent, and the total addition amount of the auxiliary agent is 0.1-2% of the total mass of the system.
The isocyanate is 4, 4-diphenylmethane diisocyanate.
The polyol compound is a mixture of terephthalic acid polyester diol and adipic acid polyester diol, and the mass ratio of the terephthalic acid polyester polyol to the adipic acid polyester diol is 0-2: 1. Further, the polyol compound is a mixture of terephthalic acid polyester diol and adipic acid polyester diol having a molecular weight of 1000-4000.
The binary arylamine compound is one or more of 3,3 ' -dichloro-4, 4 ' -diphenylmethanediamine (MOCA), 3, 5-dimethylthiotoluenediamine (DMTDA), 3, 5-diethyltoluenediamine (DETDDA), 4 ' -bis-sec-butylaminodiphenylmethane and 1, 4-bis-sec-butylaminobenzene with the molecular weight of 150-.
The dihydric alcohol chain extender is one or more of ethylene glycol, 1, 4-butanediol and neopentyl glycol with molecular weight of 62-200.
Further, the molar ratio of the polyol compound to the glycol chain extender is 1: 3-5; the molar ratio of isocyanic acid radical to hydroxyl radical in isocyanate is 1-1.05: 1, wherein the hydroxyl is the sum of hydroxyl in a polyol compound and a glycol chain extender.
Further, the catalyst is preferably an organic bismuth-based catalyst.
The antioxidant is one or two of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (antioxidant 1-1010) and 2,2' -methylene bis (4-methyl-6-tert-butylphenol) (antioxidant 2246).
The total mass of the system refers to the total mass of all raw materials, including the solvent.
The invention relates to a preparation method of arylamine modified wet polyurethane resin for space leather, which comprises the following steps:
step 1: adding part of isocyanate (accounting for 30-40 percent of the total amount of the isocyanate), part of polyol compound, part of diol chain extender (accounting for 10-20 percent of the diol chain extender) and antioxidant into a solvent, and reacting at 75-85 ℃ for 1-2h, wherein the solid content of a reaction solution is controlled to be 40-60 percent;
step 2: 5-10% of isocyanate is added into the reaction system in the step 1 for prepolymerization reaction, and the reaction is carried out for 1-3h at 75-85 ℃ in the presence of a catalyst to obtain a prepolymer, wherein the solid content of the prepolymer is controlled to be 45-60%, and the viscosity is controlled to be 40000-60000cps/75 ℃;
and step 3: and (3) adding the rest of polyol compound, diarylamine compound, the rest of diol chain extender and the rest of isocyanate into the prepolymer obtained in the step (2), stirring uniformly, continuing to react for 2-5h at 75-85 ℃, supplementing a solvent into the system according to the reaction degree in the reaction process, adding negative catalyst phosphoric acid, reaction terminator methanol and an auxiliary agent after the reaction is finished, and controlling the viscosity at 150000-250000cps/25 ℃ to obtain the polyurethane resin.
The solvent is N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC).
The molar weight ratio of the isocyanic acid group in the isocyanate added in the step 1 to the hydroxyl group in the polyol compound is 0.85-0.95: 1;
in the step 1, the addition amount of the antioxidant is 0-0.1% of the total mass of the raw materials; the addition amount of the antioxidant is counted into the addition amount of the auxiliary agent. The total mass of the antioxidant added in the preparation process is 0-0.2% of the total mass of the raw materials.
In the step 2, the molar weight ratio of the isocyanic acid radical in the supplementary isocyanate to the hydroxyl in the polyol compound is 0.90-1.1: 1.
in the step 3, the mass ratio of the diarylamine compound to the glycol chain extender is 1: 3-6.
The reaction mechanism of the invention is as follows: the special aromatic amine is adopted for modification, the resin is different from the common polyester type wet polyurethane resin in that the aromatic amine is introduced for modification, the introduction of the aromatic amine and isocyanate raw materials form a polyurea structure, and the polyurea structure has stronger polarity and more stable structure. Therefore, the formed molecular chain crystallization micro-area structure is smaller and more regular, and the physical property and the strength shown after the leather is made are higher, and the weather resistance and the hydrolysis resistance stability are better.
The system, unless otherwise noted, refers to the total weight of all materials.
The invention has the following beneficial effects:
1. the aromatic amine adopted by the polyurethane resin has two benzene rings in the molecular structure, and the generated carbamido has stronger polarity and can endow the polyurethane synthetic leather with higher strength.
2. The polyurethane resin adopts arylamine to form carbamido, so that the stability of the polyurethane resin is better, and the formed leather product has higher weather resistance and hydrolysis resistance.
3. The polyurethane resin adopts arylamine, and the arylamine chain extender has low moisture sensitivity, can be used for TDI and MDI formulas, and has longer applicability.
4. The polyurethane resin of the invention adopts special aromatic amine, which has higher strength, impact resistance and low-temperature performance and lower hardness.
5. The special arylamine adopted by the polyurethane resin has lower toxicity compared with common polyurethane amines such as MDA, HMDA and the like.
6. The invention selects organic bismuth as a reaction catalyst, wherein the environmental protection property of the organic bismuth is better than that of organic tin, which is known in the industry.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The polyester polyol with molecular weight of 2000 prepared by using PET-2 as raw materials, namely adipic acid, ethylene glycol and 1, 4-butanediol, which is used in the following embodiment can be a product with a brand name of CMA-244 produced by Nicotiana China chemical industry Co., Ltd or a product with a brand name of POL-2356 produced by Qingdao Xingyan chemical industry Co., Ltd; PET-4 is polyester polyol with the molecular weight of 4000 prepared by adipic acid, ethylene glycol and 1, 4-butanediol which are used as raw materials, and a product with the brand of CMA-244 and 4000 produced by Nicotiana China chemical industry Co., Ltd, or a product with the brand of POL-2328 produced by Qingdao Xingyan chemical industry Co., Ltd;
the special polyester polyol PET-2T is polyester polyol with the molecular weight of 2000 prepared by taking adipic acid, terephthalic acid, 1, 4-butanediol, 1, 6-hexanediol and the like as raw materials; the product of Raynol PL-2000 brand produced by Qingdao Ruinoo chemical industry Co., Ltd or the product of POL-1856 brand produced by Qingdao Xingytian chemical industry Co., Ltd can be used;
EG is ethylene glycol;
MDI is 4, 4' -diphenylmethane diisocyanate;
organic bismuth and phosphoric acid are respectively used as a positive catalyst and a negative catalyst for reaction, wherein the environmental protection property of the organic bismuth is better than that of organic tin, which is known in the industry;
DMF is solvent dimethylformamide, and methanol is reaction terminator.
Example 1:
(1) 200g of polyol compound PET-4, 300g of polyol compound PET-2T, 5g of ethylene glycol and 3g of antioxidant I-1010 are added into 500g of DMF solvent;
(2) uniformly stirring the solution in the step (1), adding 60g of diisocyanate, and reacting at 75 ℃ for 1h in the presence of 0.8g of catalyst organic bismuth Mb 20;
(3) adding about 10g of diisocyanate into the mixture obtained in the step (2), and carrying out prepolymerization reaction for 2 hours at 75 ℃ to obtain a prepolymer;
(4) adding 1200g of DMF (dimethyl formamide) solvent, 30g of ethylene glycol, 10g of diarylamine and 100g of diisocyanate into the prepolymer, uniformly stirring, and continuously reacting for 5 hours at 75 ℃; after the reaction is finished, adding a reaction terminator methanol, and controlling the viscosity of the mixture at 200-300Pas/25 ℃ to obtain the polyurethane resin.
Example 2:
this example 2 was prepared in the same manner as in example 1 except that "the solvent DMF 1200g, ethylene glycol 30g, diarylamine 10g and diisocyanate 100g were added to the prepolymer" the solvent DMF 1200g, ethylene glycol 31g, diarylamine 5g and diisocyanate 100g were added to the prepolymer ".
Example 3:
this example 3 was prepared in the same manner as in example 1 except that "the solvent DMF 1200g, ethylene glycol 30g, diarylamine 10g and diisocyanate 100g were added to the prepolymer" the solvent DMF 1200g, ethylene glycol 28g, diarylamine 20g and diisocyanate 100g were added to the prepolymer ".
Comparative example 1:
comparative example 1 was prepared in the same manner as in example 1 except that "the addition of 1200g of DMF solvent, 30g of ethylene glycol, 10g of diarylamine and 100g of diisocyanate to the prepolymer" was adjusted to "the addition of 1200g of DMF solvent, 32g of ethylene glycol and 100g of diisocyanate to the prepolymer".
The tensile modulus and peel strength of the polyurethane resin prepared in example 1 were compared with those of comparative example 1 in the following table:
the stress Se100 of the involucra stretching in the upper surface and the involucra stretching in the middle surface is 100 percent of tensile modulus;
hydrolysis resistance test in the table above-peel strength retention is: the ratio of the tested peel strength to the original leather peel strength after being placed for 7 days under the conditions of 70 ℃ of temperature and 95% of humidity.
The hydrolysis resistance test in the above table II deflection test is as follows: after being placed at 70 ℃ and 95% humidity for 7 days, the leather sample was subjected to a flex test at 25 ℃ for 10 ten thousand times.
As can be seen from the above table, the 100% tensile modulus of example 1 is significantly lower than that of comparative example 1 at the same hard segment content, thus demonstrating that the specific aromatic amine employed in the polyurethane resin of the present invention can have lower hardness while having higher strength, impact resistance, and low-temperature properties.
As can be seen from the above table, the peel strength of example 1 is about 30% higher than that of comparative example 1 under the same content of hard segments and soft segments, thereby proving that the aromatic amine used in the polyurethane resin of the present invention has two benzene rings in the molecular structure thereof, and the generated urea groups have stronger polarity, and can give higher strength to the polyurethane synthetic leather.
As can be seen from the above table, the peel strength of example 3 is about 10N higher than that of example 1, and the peel strength of example 1 is about 20N higher than that of example 2 under the same hard block and soft block contents, thus proving that the binary aromatic amine used in the polyurethane resin of the present invention has a positive correlation between the usage amount and the peel strength of the synthetic leather prepared from the binary aromatic amine within a certain range. The peel retention of example 3 is 3% higher than that of example 1, and the peel retention of example 1 is 12% higher than that of example 2, thus demonstrating that the usage amount of the diarylamine used in the polyurethane resin of the present invention is in positive correlation with the hydrolysis resistance of the synthetic leather prepared from the diarylamine within a certain range.
As can be seen from the table above, testing a peel strength retention, example 1 was 26% higher than comparative example 1; hydrolysis resistance test two flex tests, the leather surface of example 1 is not cracked, and the leather surface of the two-to-two proportion 1 is cracked, so that the polyurethane resin adopts the arylamine to form the carbamido, the stability of the polyurethane resin is better, and the formed leather product has higher weather resistance and hydrolysis resistance.
The basic principles of the present invention, the characteristics of the resin, and the advantages of the present invention have been described above. The foregoing embodiments and description have been provided merely to illustrate the principles of the invention and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The arylamine modified wet polyurethane resin for the space leather is characterized by comprising the following raw materials in parts by weight:
isocyanate, the amount of which accounts for 5-10% of the total mass of the system;
the polyol compound accounts for 15-25% of the total weight of the system;
the dosage of the binary arylamine compound accounts for 0-3% of the total mass of the system;
the using amount of the dihydric alcohol chain extender accounts for 1 to 3 percent of the total mass of the system;
the catalyst is organic tin catalyst or organic bismuth catalyst, and the amount of the catalyst is 0.001-0.05% of the mass of the polyalcohol compound;
the adding amount of the negative catalyst phosphoric acid is 0 to 0.001 percent of the total mass of the system;
the addition amount of methanol as a reaction terminator is 0.005-0.015 percent of the total mass of the system;
the auxiliary agent is one or more of surfactant, antioxidant, ultraviolet absorbent, weather-resistant stabilizer, waterproof decomposer and anti-sticking agent, and the total addition amount of the auxiliary agent is 0.1-2% of the total mass of the system.
2. The aromatic amine modified wet-process polyurethane resin for space leather according to claim 1, characterized in that:
the polyol compound is a mixture of terephthalic acid polyester diol and adipic acid polyester diol, and the mass ratio of the terephthalic acid polyester polyol to the adipic acid polyester diol is 0-2: 1.
3. The aromatic amine modified wet-process polyurethane resin for space leather according to claim 2, characterized in that:
the polyol compound is a mixture of terephthalic acid polyester diol with the molecular weight of 1000-4000 and adipic acid polyester diol.
4. The aromatic amine modified wet-process polyurethane resin for space leather according to claim 1, characterized in that:
the binary arylamine compound is one or more of 3,3 ' -dichloro-4, 4 ' -diphenylmethane diamine with molecular weight of 150-400, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 4 ' -bis-sec-butylaminodiphenylmethane and 1, 4-bis-sec-butylaminobenzene.
5. The aromatic amine modified wet-process polyurethane resin for space leather according to claim 1, characterized in that:
the dihydric alcohol chain extender is one or more of ethylene glycol, 1, 4-butanediol and neopentyl glycol with molecular weight of 62-200.
6. The arylamine-modified wet-process polyurethane resin for space leather as claimed in claim 1, 2 or 5, wherein:
the molar ratio of the polyol compound to the glycol chain extender is 1: 3-5; the molar ratio of isocyanic acid radical to hydroxyl radical in isocyanate is 1-1.05: 1, wherein the hydroxyl is the sum of hydroxyl in a polyol compound and a glycol chain extender.
7. The aromatic amine modified wet-process polyurethane resin for space leather according to claim 1, characterized in that:
the antioxidant is one or two of 1-1010 antioxidant and 2246 antioxidant.
8. A preparation method of the wet-process polyurethane resin for the arylamine modified space leather, which is described in any one of claims 1 to 5, is characterized by comprising the following steps:
step 1: adding part of isocyanate, part of polyol compound, part of diol chain extender and antioxidant into a solvent, and reacting at 75-85 ℃ for 1-2h, wherein the solid content of the reaction solution is controlled at 40-60%;
step 2: 5-10% of isocyanate is added into the reaction system in the step 1 for prepolymerization reaction, and the reaction is carried out for 1-3h at 75-85 ℃ in the presence of a catalyst to obtain a prepolymer, wherein the solid content of the prepolymer is controlled to be 45-60%, and the viscosity is controlled to be 40000-60000cps/75 ℃;
and step 3: and (3) adding the rest of polyol compound, diarylamine compound, the rest of diol chain extender and the rest of isocyanate into the prepolymer obtained in the step (2), stirring uniformly, continuing to react for 2-5h at 75-85 ℃, supplementing a solvent into the system according to the reaction degree in the reaction process, adding negative catalyst phosphoric acid, reaction terminator methanol and an auxiliary agent after the reaction is finished, and controlling the viscosity at 150000-250000cps/25 ℃ to obtain the polyurethane resin.
9. The method of claim 8, wherein:
the molar weight ratio of the isocyanic acid group in the isocyanate added in the step 1 to the hydroxyl group in the polyol compound is 0.85-0.95: 1; the molar weight ratio of isocyanic acid radical in the supplementary isocyanate in the step 2 to hydroxyl in the polyol compound is 0.90-1.1: 1.
10. the method of claim 8, wherein:
in the step 3, the mass ratio of the diarylamine compound to the glycol chain extender is 1: 3-6.
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2020
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