CN114805738B - Wet polyurethane resin and preparation method thereof - Google Patents

Wet polyurethane resin and preparation method thereof Download PDF

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Publication number
CN114805738B
CN114805738B CN202210638571.2A CN202210638571A CN114805738B CN 114805738 B CN114805738 B CN 114805738B CN 202210638571 A CN202210638571 A CN 202210638571A CN 114805738 B CN114805738 B CN 114805738B
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polyol
diisocyanate
acid
polyurethane resin
glycol
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CN114805738A (en
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杨信实
朱彦
张初银
彭超豪
彭峰
方飞
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Zhejiang Huafon Synthetic Resin Co ltd
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Zhejiang Huafon Synthetic Resin Co ltd
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a wet polyurethane resin and a preparation method thereof, wherein the polyurethane resin comprises the following raw material components in percentage by weight: 4% -12% of diisocyanate; 18% -22% of polyester polyol; 0.5 to 2 percent of chain extender; and the balance of solvent; the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate. The polyester polyol is one or more of at least one C2-C10 dibasic acid and at least two C2-C10 dihydric alcohols obtained by polymerization; the average number average molecular weight of the polyester polyol is 2000-4000. The chain extender comprises more than one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol. The synthetic leather prepared from the wet polyurethane resin has the characteristics of good comfort, excellent anti-skid property and excellent hygroscopicity.

Description

Wet polyurethane resin and preparation method thereof
Technical Field
The invention particularly relates to wet polyurethane resin and a preparation method and application thereof, and belongs to the technical field of polyurethane resin preparation.
Background
At present, polyurethane synthetic leather is widely applied to the fields of clothing, furniture, shoe materials and the like, and along with the development of the body-building sports industry in recent years, indoor sports including yoga, shuttlecocks and the like are increasingly popular, and the synthetic leather is gradually applied to corresponding sports equipment, such as grip leather on a badminton racket, polyurethane yoga mats and the like.
Compared with polyurethane synthetic leather applied to other fields, yoga mat surface leather and grip leather have higher requirements on skid resistance, hygroscopicity and comfort of leather due to direct contact with skin. However, the polyurethane material for leather at present needs low-modulus polyurethane for maintaining good touch feeling of synthetic leather due to technical barriers, however, for wet polyurethane resin, the low-modulus resin is difficult to form vertical-shaped cells in the solidification process, and the cell structure is just the guarantee of strong moisture absorption performance of the synthetic leather, so that the polyurethane synthetic leather is difficult to simultaneously achieve excellent moisture absorption and comfortable touch feeling, and the application of the polyurethane synthetic leather to sports equipment is greatly limited.
Disclosure of Invention
Technical problems: aiming at the defects of the prior art, the invention aims to provide wet polyurethane resin, a preparation method and application thereof, and synthetic leather prepared from the wet polyurethane resin has the characteristics of good comfort, excellent skid resistance and excellent hygroscopicity.
The technical scheme is as follows: the wet polyurethane resin provided by the invention comprises the following raw material components in percentage by weight:
the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
The polyester polyol is one or more of at least one C2-C10 dibasic acid and at least two C2-C10 dihydric alcohols obtained by polymerization; the average number average molecular weight of the polyester polyol is 2000-4000.
The chain extender comprises more than one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol.
The dibasic acid has 3-8 carbon atoms and comprises one or more of aliphatic dibasic acid, alicyclic dibasic acid or aromatic dibasic acid.
Further, the aliphatic dibasic acid is linear aliphatic dibasic acid, and comprises one or more of malonic acid, succinic acid, glutaric acid and adipic acid.
Further, the cycloaliphatic diacid includes cyclohexanedicarboxylic acid.
Further, the aromatic dibasic acid comprises phthalic acid.
The dihydric alcohol has 2-8 carbon atoms and comprises more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and diethylene glycol.
The solvent may be an oil solvent known in the art, including N, N-dimethylformamide DMF and/or dimethylacetamide DMAC.
The wet polyurethane resin also comprises 2-5% of polyol auxiliary agent by weight percent.
The polyol auxiliary agent comprises more than one of polyether polyol and rosin ester polyol; the polyol auxiliary agent is in a free state in the polyurethane resin.
The polyether polyol comprises one or more of amino-terminated polyoxyethylene ether, amino-terminated polyoxypropylene ether, hydroxyl-terminated polyoxyethylene ether or hydroxyl-terminated polyoxypropylene ether, the average functionality is 2-3, and the average number average molecular weight is 2000-4000 g/mol.
The rosin ester polyol has an average functionality of 2 and an average number average molecular weight of 3000-4000 g/mol.
The wet process polyurethane resin preparation process includes the reaction of diisocyanate, polyester polyol and chain extender in the presence of solvent;
the preparation method can be used for directly and fully mixing and reacting the components comprising diisocyanate, polyester polyol and chain extender in the presence of a solvent to obtain polyurethane resin; or the prepolymer is obtained by pre-polymerizing part of diisocyanate and polyester polyol in the presence of a solvent, and then reacting the prepolymer with the rest of diisocyanate and a chain extender.
If a polyol auxiliary agent is further added, the polyol auxiliary agent is added after diisocyanate, polyester polyol and chain extender are fully reacted and blocked, so that the polyol auxiliary agent is ensured to exist in the polyurethane resin in a free state.
"blocked" in the present invention means that the polyurethane resin does not contain residual isocyanate groups.
The polyurethane resin can be prepared into synthetic leather by adopting a wet process known in the art, and can be applied to the fields of sports equipment such as yoga mat surface leather, grip leather and the like.
The beneficial effects are that: the wet polyurethane resin provided by the invention has comfortable hand feeling and excellent anti-skid property and hygroscopicity through the synergistic combination of diisocyanate, polyester polyol and chain extender, and the synthetic leather prepared from the polyurethane resin can be applied to the synthetic leather for sports equipment which needs to be directly contacted with skin. More surprisingly, the incorporation of a small amount of free polyol aid in the polyurethane resin further improves the overall properties of the synthetic leather.
Detailed Description
The wet polyurethane resin provided by the invention comprises the following raw material components in percentage by weight:
the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and isomers and/or derivatives and/or modified polymers thereof.
The polyester polyol is one or more of at least one C2-C10 dibasic acid and at least two C2-C10 dihydric alcohols obtained by polymerization;
further, the polyester polyol is two or more of polyester polyols obtained by polymerizing at least one C2-C10 dibasic acid and at least two C2-C10 dihydric alcohols;
the average number average molecular weight of the polyester polyol is 2000-4000;
further, the dibasic acid has 3-8 carbon atoms and comprises one or more of aliphatic dibasic acid, alicyclic dibasic acid or aromatic dibasic acid.
Further, the aliphatic dibasic acid is linear aliphatic dibasic acid, and comprises one or more of malonic acid, succinic acid, glutaric acid and adipic acid.
Further, the cycloaliphatic diacid includes cyclohexanedicarboxylic acid.
Further, the aromatic dibasic acid comprises phthalic acid.
Preferably, the dihydric alcohol has 2-8 carbon atoms and comprises more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and diethylene glycol;
as an example, the dibasic acid is one or more of glutaric acid, adipic acid, cyclohexanedicarboxylic acid and phthalic acid;
as an example, the dihydric alcohol is more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and diethylene glycol;
by way of example, the polyester polyols include polyglutaric acid-ethylene glycol-propylene glycol ester polyol, polyglutaric acid-ethylene glycol-butylene glycol ester polyol, polyglutaric acid-ethylene glycol-pentylene glycol ester polyol, polyglutaric acid-ethylene glycol-hexylene glycol ester polyol, polyglutaric acid-ethylene glycol-diethylene glycol ester polyol, polyglutaric acid-propylene glycol-diethylene glycol ester polyol, polyglutaric acid-butylene glycol-diethylene glycol ester polyol, polyglutaric acid-pentylene glycol-diethylene glycol ester polyol, polyaspartic acid-ethylene glycol-propylene glycol ester polyol, polyaspartic acid-ethylene glycol-butylene glycol ester polyol, polyaspartic acid-ethylene glycol-pentylene glycol ester polyol, a polyadipic acid-ethylene glycol-hexanediol ester polyol, a polyadipic acid-ethylene glycol-diethylene glycol ester polyol, a polyadipic acid-propylene glycol-diethylene glycol ester polyol, a polyadipic acid-pentanediol-diethylene glycol ester polyol, a polyadipic acid-ethylene glycol-propylene glycol ester polyol, a polyadipic acid-ethylene glycol-butanediol ester polyol, a polyadipic acid-ethylene glycol-pentanediol ester polyol, a polyadipic acid-ethylene glycol-hexanediol ester polyol, a polyadipic acid-ethylene glycol-diethylene glycol ester polyol, a polyadipic acid-propylene glycol-diethylene glycol ester polyol, polybutylene terephthalate-diethylene glycol ester polyol, polybutylene terephthalate-pentanediol-diethylene glycol ester polyol, polycyclohexane dicarboxylic acid-ethylene glycol-propylene glycol ester polyol, polycyclohexane dicarboxylic acid-ethylene glycol-butanediol ester polyol, polycyclohexane dicarboxylic acid-ethylene glycol-pentanediol ester polyol, polycyclohexane dicarboxylic acid-ethylene glycol-hexanediol ester polyol, one or more of a polycyclohexane dicarboxylic acid-ethylene glycol-diethylene glycol ester polyol, a polycyclohexane dicarboxylic acid-propylene glycol-diethylene glycol ester polyol, a polycyclohexane dicarboxylic acid-butylene glycol-diethylene glycol ester polyol, and a polycyclohexane dicarboxylic acid-pentylene glycol-diethylene glycol ester polyol;
further, the polyester polyol has an aliphatic linear structure and does not contain a branched chain, an aromatic structure or a cyclic structure;
more preferably, the dibasic acid is a linear aliphatic dibasic acid, including more than one of malonic acid, succinic acid, glutaric acid and adipic acid;
in some examples of the invention, the polyester polyol comprises one or more of a poly (ethylene glycol-propylene glycol) ester polyol, a poly (ethylene glycol-butylene glycol) ester polyol, a poly (ethylene glycol-hexylene glycol) ester polyol, a poly (ethylene glycol-diethylene glycol) ester polyol, a poly (propylene glycol-diethylene glycol) ester polyol, a poly (butylene glycol-diethylene glycol) ester polyol, a poly (pentylene glycol-diethylene glycol) ester polyol, a poly (adipic acid-ethylene glycol-propylene glycol) ester polyol, a poly (adipic acid-ethylene glycol-butylene glycol) ester polyol, a poly (adipic acid-ethylene glycol-hexylene glycol) ester polyol, a poly (adipic acid-ethylene glycol-diethylene glycol) ester polyol, a poly (adipic acid-propylene glycol-diethylene glycol) ester polyol, a poly (adipic acid-butylene glycol-diethylene glycol-monoglycol) ester polyol, and the like;
still further, in some embodiments of the present invention, the polyester polyol is a combination of two polyester polyols in a mass ratio of 8:2 to 6:5;
the chain extender comprises more than one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol;
the solvent is N, N-dimethylformamide DMF and/or dimethylacetamide DMAC;
by way of example, the solvent of the present invention is DMF.
Further, the wet polyurethane resin also comprises 2 to 5 weight percent of polyol auxiliary agent;
the polyol auxiliary agent comprises more than one of polyether polyol and rosin ester polyol;
the polyether polyol comprises more than one of amino-terminated polyoxyethylene ether, amino-terminated polyoxypropylene ether, hydroxyl-terminated polyoxyethylene ether and hydroxyl-terminated polyoxypropylene ether, the average functionality is 2-3, and the average number average molecular weight is 2000-4000 g/mol;
the rosin ester polyol has an average functionality of 2 and an average number average molecular weight of 3000-4000 g/mol.
The wet polyurethane resin preparation method comprises the steps of fully reacting diisocyanate, polyester polyol and chain extender in the presence of a solvent to obtain the polyurethane resin;
the preparation method can be used for directly and fully mixing and reacting the components comprising diisocyanate, polyester polyol and chain extender in the presence of a solvent to obtain polyurethane resin; or the prepolymer is obtained by pre-polymerizing part of diisocyanate and polyester polyol in the presence of a solvent, and then reacting the prepolymer with the rest of diisocyanate and a chain extender.
If a polyol auxiliary agent is further added, the polyol auxiliary agent is added after diisocyanate, polyester polyol and chain extender are fully reacted and blocked, so that the polyol auxiliary agent is ensured to exist in the polyurethane resin in a free state.
"blocked" in the present invention means that the polyurethane resin does not contain residual isocyanate groups;
in some examples of the invention, residual isocyanate groups may be blocked by controlling the total molar amount of isocyanate groups in the polyurethane to be slightly higher than the total molar amount of isocyanate groups, for example controlling the ratio of isocyanate groups to the molar amount of isocyanate groups reactive to isocyanate groups to be 1: 1.005-1; 1.05;
in other examples of the invention, chain blocking agents may be added to block residual isocyanate groups, such as small molecule monohydric alcohols, including more than one of methanol, ethanol, isopropanol.
In the embodiment of the invention, the wet polyurethane resin preparation method is prepared by a prepolymerization method and specifically comprises the following steps:
step 1, fully reacting diisocyanate and polyester polyol in the presence of a solvent to obtain a prepolymer, controlling the reaction temperature to be 70-80 ℃, and controlling the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid to be 0.6:1-0.8:1, wherein the reaction of the reaction liquid is finished without residual isocyanate groups; the solid content of the prepolymer solution is 30% -65%;
step 2, adding a chain extender and a solvent into the prepolymer solution, preserving heat for 0.2-0.5 h at 50-60 ℃, adding diisocyanate, fully reacting at 70-80 ℃, and controlling the mole ratio of isocyanate groups to hydroxyl groups in the reaction solution to be 1-1: 1.09, fully reacting diisocyanate, polyester polyol and a chain extender to obtain polyurethane resin; the solid content of the polyurethane resin is 20% -40%.
Preferably, the chain-blocking agent is added after the reaction of the prepolymer with the chain extender and diisocyanate in step (2) to react off residual isocyanate groups. Preferably, the preparation process may be carried out in the presence of a catalyst known in the art to accelerate the reaction rate.
In some embodiments of the invention, the catalyst is an organotin-based catalyst;
the addition amount of the chain blocking agent and the catalyst is not particularly limited, and the chain blocking agent and the catalyst can be added according to the conventional dosage in the field;
further, in some embodiments of the invention, the polyol aid is added after the diisocyanate has been fully reacted with the polyester polyol and the chain extender and capped.
Illustratively, the polyol additive is added after the chain sealer is added to block the residual isocyanate groups.
The present invention is further illustrated by the following examples, in which specific material ratios, preparation processes, results, etc. are described only for illustrating the present invention, but not for limiting the scope of the present invention, and all equivalent changes or modifications according to the essence of the present invention should be included in the scope of the present invention.
Example 1
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, the polyester polyol is 6 percent by weight of polyaspartic acid-ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 12 percent by weight of polyadipic acid-propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol; the polyol auxiliary agent is amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3).
Example 2
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is poly (glutaric acid) -ethylene glycol-pentanediol ester polyol (average molecular weight 4000) accounting for 8% by weight and poly (glutaric acid) -propylene glycol-diethylene glycol ester polyol (average molecular weight 4000) accounting for 12% by weight; the chain extender is glycol; the polyol aid is a rosin ester polyol (average molecular weight 3000, average functionality 2).
Example 3
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 10% by weight of poly (adipic acid) -ethylene glycol-butylene glycol ester polyol (average molecular weight 2500) and 12% by weight of poly (glutaric acid) -ethylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol; the polyol auxiliary agent is hydroxyl-terminated polyoxyethylene ether (average molecular weight 4000, average functionality 3).
Example 4
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, the polyester polyol is 6 percent by weight of polyaspartic acid-ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 16 percent by weight of polyadipic acid-propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is glycol; the polyol auxiliary agent is amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3).
Example 5
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate and the polyester polyol is polyglutaric acid-ethylene glycol-pentanediol ester polyol (average molecular weight 4000); the chain extender is glycol; the polyol aid is a rosin ester polyol (average molecular weight 3000, average functionality 2).
Example 6
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, the polyester polyol is 7.5 percent by weight of polyazelaic acid-ethylene glycol-butanediol ester polyol (average molecular weight 2500) and 11 percent by weight of polybutylene phthalate-butanediol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is hexanediol; the polyol auxiliary agent is 2% by weight of an amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3) and 3% by weight of a hydroxyl-terminated polyoxyethylene ether (average molecular weight 4000, average functionality 3).
Example 7
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, the polyester polyol is 7.5 percent by weight of poly adipic acid-ethylene glycol-butylene glycol ester polyol (average molecular weight 2500) and 11 percent by weight of poly cyclohexane dicarboxylic acid-ethylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is hexanediol; the polyol auxiliary agent is 2% by weight of an amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3) and 3% by weight of a hydroxyl-terminated polyoxyethylene ether (average molecular weight 4000, average functionality 3).
Example 8
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 6% by weight of poly (adipic acid-propylene glycol ester) polyol (average molecular weight 2000) and 12% by weight of poly (adipic acid-diethylene glycol ester) polyol (average molecular weight 2000); the chain extender is butanediol; the polyol auxiliary agent is amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3).
Example 9
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 6% by weight of poly (adipic acid) -ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 12% by weight of poly (adipic acid) -propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol.
Example 10
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 6% by weight of poly (adipic acid) -ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 12% by weight of poly (adipic acid) -propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol; the polyol auxiliary agent is amino-terminated polyoxypropylene ether (average molecular weight 3500, average functionality 3).
Example 11
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 6% by weight of poly (adipic acid) -ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 12% by weight of poly (adipic acid) -propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol; the polyol aid is polytetrahydrofuran ether polyol (average molecular weight 3500, average functionality 3).
Example 12
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate, and the polyester polyol is 6% by weight of poly (adipic acid) -ethylene glycol-propylene glycol ester polyol (average molecular weight 2000) and 12% by weight of poly (adipic acid) -propylene glycol-diethylene glycol ester polyol (average molecular weight 2000); the chain extender is butanediol; the polyol auxiliary agent is hydroxyl silicone oil (average molecular weight 3500, average functionality 3).
Comparative example 1
Comprises the following raw material components in percentage by weight:
wherein the diisocyanate is diphenylmethane diisocyanate and the polyester polyol is polyoxyethylene-oxypropylene polyol (average molecular weight 4000); the chain extender is glycol; the polyol aid is a rosin ester polyol (average molecular weight 3000, average functionality 2).
Preparation of polyurethane resin:
polyurethane resin 1
(1) According to the raw material component proportion of the example 1, diisocyanate and polyester polyol are fully reacted in the presence of DMF to obtain a prepolymer, the reaction temperature is controlled to be 80 ℃, and the reaction of the reaction solution without residual isocyanate groups is finished;
(2) Adding a chain extender and DMF into the prepolymer solution, preserving heat at 50 ℃, adding diisocyanate, fully reacting at 80 ℃, and controlling the mole ratio of isocyanate groups to hydroxyl groups in the reaction solution to be 1-1: 1.09, finally obtaining polyurethane resin;
after the prepolymer in the step (2) reacts with the chain extender and the diisocyanate, adding a chain sealing agent to react to remove residual isocyanate groups, and adding a polyol auxiliary agent.
Examples 2 to 9 and examples 11 to 12, the polyurethane resin preparation method of comparative example 1 was consistent with example 1, and polyurethane resins 2 to 8, polyurethane resins 11 to 12, and comparative polyurethane resin 1 were obtained, respectively;
the preparation method of example 10 is different from the preparation method of polyurethane resin of example 1 in that the polyol auxiliary agent is added simultaneously with the chain extender in step (2), so that the polyol auxiliary agent is not present in the polyurethane resin in a free form.
Preparation of synthetic leather bass: polyurethane resin 1 to 12, comparative polyurethane resin 1 was coated on a BASE fabric, and Bass (BASE) was obtained by a wet process.
The prepared bass 1 to 12 and the comparative bass 1 are respectively subjected to the following performance tests:
(1) Hand feeling: the hand feeling comfort level is judged by touching the bass by hand, the hand feeling comfort level is expressed by 'more and better', preferably 'worst';
(2) Water absorption: 1uL of water is dripped by a 1uL needle tube to the surface of the bass and then is vertically placed, and the time for drying the water trace is recorded and calculated as s;
(3) Slip resistance: the anti-slip effect is determined by touching the bass with a hand and slowly sliding with the same force, and is indicated by "", preferably "", and worst "".
The performance test performance is as follows:
polyurethane bass Hand feel Water absorption Slip resistance
Bass 1 **** 21 *****
Bass 2 **** 23 *****
Bass 3 ***** 16 *****
Bass 4 ***** 19 *****
Bass 5 **** 30 ****
Bass 6 *** 40 ****
Bass 7 *** 38 ****
Bass 8 *** 32 ****
Bass 9 *** 45 ****
Bass 10 ** 42 ****
Bass 11 *** 38 ****
Bass 12 **** 40 ***
Comparative bass 1 ** 35 ****

Claims (4)

1. The wet polyurethane resin is characterized by comprising the following raw material components in percentage by weight:
4% -12% of diisocyanate;
18% -22% of polyester polyol;
0.5% -2% of chain extender;
2% -5% of a polyol auxiliary agent; and
the balance of solvent;
the polyester polyol is two combinations of polyadipic acid-ethylene glycol-propylene glycol ester polyol, polyadipic acid-propylene glycol-diethylene glycol ester polyol, polyglutaric acid-ethylene glycol-pentanediol ester polyol, polyglutaric acid-propylene glycol-diethylene glycol ester polyol, polyadipic acid-ethylene glycol-butanediol ester polyol and polyglutaric acid-ethylene glycol-diethylene glycol ester polyol; the mass ratio of the polyester polyol is 8:2-6:5;
the polyol auxiliary agent is more than one of polyether polyol and rosin ester polyol; the polyol auxiliary agent is in a free state in the polyurethane resin; the polyether polyol comprises one or more of amino-terminated polyoxyethylene ether, amino-terminated polyoxypropylene ether, hydroxyl-terminated polyoxyethylene ether or hydroxyl-terminated polyoxypropylene ether, the average functionality is 2-3, and the average number average molecular weight is 2000-4000 g/mol.
2. The wet polyurethane resin according to claim 1, wherein the polyester polyol has an average molecular weight of 2000 to 4000.
3. The wet polyurethane resin according to claim 1, wherein the rosin ester polyol has an average functionality of 2 and an average molecular weight of 3000 to 4000g/mol.
4. The wet polyurethane resin according to claim 1, wherein the chain extender comprises more than one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol; the diisocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate; the solvent is N, N-dimethylformamide DMF and/or dimethylacetamide DMAC.
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