CN109575232A - A kind of no-solvent type aqueous polyurethane of high-tensile and preparation method thereof - Google Patents

A kind of no-solvent type aqueous polyurethane of high-tensile and preparation method thereof Download PDF

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CN109575232A
CN109575232A CN201811504064.XA CN201811504064A CN109575232A CN 109575232 A CN109575232 A CN 109575232A CN 201811504064 A CN201811504064 A CN 201811504064A CN 109575232 A CN109575232 A CN 109575232A
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aqueous polyurethane
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type aqueous
bath temperature
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CN109575232B (en
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马建中
董雨菲
刘超
鲍艳
李帅
林阳
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Shaanxi University of Science and Technology
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract

The invention discloses no-solvent type aqueous polyurethane of a kind of high-tensile and preparation method thereof, technical solutions are as follows: firstly, by polymer diatomic alcohol 100~120 DEG C of vacuum drying 14h in a vacuum drying oven;Polymer diatomic alcohol after re-dry pours into three-necked flask and adds diisocyanate, and setting bath temperature is 70~85 DEG C, stirs 2~3h;Then, bath temperature is reduced to 60~70 DEG C, 2,2- dimethylolpropionic acid is added into reaction solution, stir 1.5~2.5h;Then, bath temperature is reduced to 45~55 DEG C, neutralizer is added into reaction solution, stir 20~45min;Finally, bath temperature is reduced to 25~30 DEG C again, deionized water is added into reaction solution, 30~60min of high-speed stirred obtains no-solvent type aqueous polyurethane.Preparation method provided by the present invention is easy to operate, synthesis cost is cheap, the no-solvent type aqueous polyurethane mechanical property with higher of preparation.

Description

A kind of no-solvent type aqueous polyurethane of high-tensile and preparation method thereof
Technical field
The invention belongs to aqueous polyurethane fabricating technology fields, and in particular to a kind of no-solvent type of high-tensile Aqueous polyurethane and preparation method thereof.
Background technique
Aqueous polyurethane is a kind of environmentally protective, nontoxic high molecular material using water as decentralized medium.With resistance to The features such as mill property is good, processability is good, performance is adjustable, low temperature is submissive meets the performance requirement of every aspect in people's life, existing It is widely used to the fields such as leather, coating, weaving, rubber and medical material.
In the synthetic method of existing aqueous polyurethane, in order to adjust the viscosity of performed polymer dispersion stage, all can or it is more Or few use organic solvent.Although the organic solvent in system can be improved the rate of drying of lotion and improve its film forming Can, but the problems such as the presence of organic solvent not only will increase production cost but also will cause environmental pollution, be unfavorable for aqueous poly- The popularization and application of urethane.Therefore, it reduces the dosage of organic solvent to the greatest extent and is finally reached solvent free, be current aqueous polyurethane One of Main way of research.
But the mechanical property of no-solvent type aqueous polyurethane is poor, needs to improve its hard segment content to improve its mechanical property Energy.In general, under the premise of meeting cured, chain extender dosage is more, and corresponding diisocyanate dosage is also more, poly- ammonia The hard segment content of ester is high, it is hereby achieved that high-intensitive material.But this undoubtedly will increase production cost, thus explore one The preparation process for planting no-solvent type aqueous polyurethane environmentally protective, low in cost and with high-tensile is current aqueous poly- The major issue that urethane research institute faces.
Summary of the invention
The purpose of the present invention is to provide no-solvent type aqueous polyurethane of a kind of high-tensile and preparation method thereof, solutions The problems such as having determined existing aqueous polyurethane there are environmental pollution and poor mechanical properties.
Technical scheme is as follows:
A kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile, comprising the following steps:
Step 1: polymer diatomic alcohol is put into vacuum oven, 100~120 DEG C at a temperature of, carry out vacuum drying 1 ~4h;
Preferably, polymer diatomic alcohol is polytetrahydrofuran ether glycol, polycaprolactone, polycarbonate glycol, polyadipate second two One or more of mixtures of alcohol, the molecular weight of polymer diatomic alcohol are 1000.
Step 2: the polymer diatomic alcohol after will be dry in step 1 pours into three-necked flask and adds diisocyanate, Heating water bath stirring is carried out, the bath temperature that reaction system is arranged is 70~85 DEG C, and the time of stirring is 2~3h;
Preferably, diisocyanate is isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate Or polymethylene multi-phenenyl isocyanate.
Step 3: being reduced to 60~70 DEG C for the bath temperature of reaction system, adds into the resulting reaction solution of step 2 Enter 2,2- dimethylolpropionic acid, stirs 1.5~2.5h;
Step 4: being reduced to 45~55 DEG C for the bath temperature of reaction system, into step 3 resulting reaction solution in addition And agent, stir 20~45min;
Preferably, neutralizer is sodium hydroxide, ammonium hydroxide or triethylamine.
Step 5: being reduced to 25~30 DEG C for the bath temperature of reaction system, adds into the resulting reaction solution of step 4 Enter deionized water, 30~60min of high-speed stirred obtains no-solvent type aqueous polyurethane.
Preferably, Step 2: in three, four, the revolving speed of stirring is 200 ~ 400 r/min;In step 5, the revolving speed of stirring For 700 ~ 1200 r/min.
Preferably, polymer diatomic alcohol: diisocyanate: 2,2- dimethylolpropionic acids: neutralizer: the matter of deionized water Amount is than being 23 ~ 38:10 ~ 26:1.5 ~ 4.0:0.6 ~ 2.2:100 ~ 140.
The no-solvent type aqueous polyurethane and preparation method thereof of a kind of high-tensile disclosed in this invention, with existing skill Art is compared, and is had the beneficial effect that
(1) present invention provides the no-solvent type aqueous polyurethane and preparation method thereof of high-tensile, during the preparation process completely Do not add organic solvent, organic residue zero;
(2) water-base polyurethane material that the preparation method used in the present invention is prepared, the more existing aqueous polyurethane of tensile strength It significantly improves, which is about 2~3 times of the existing aqueous polyurethane in market;
(3) lower production costs of preparation method provided by the present invention are not required to that is, under the premise of meeting material performance requirement Chain extender (such as: 1,4-butanediol, ethylene glycol, ethanol amine) is used, reduce production cost;
(4) preparation method provided by the present invention is green synthesis method, easy to operate, synthesis cost is cheap and product have compared with High mechanical property.
Specific embodiment
The feature that the invention is further illustrated by the following examples, but the scope of the invention is not limited to following implementations Example.After having read the content of the invention stated, those skilled in the art can make change and modification to the present invention, these Equivalent form equally falls within the range of the application the appended claims restriction.
A kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile, comprising the following steps:
Step 1: polymer diatomic alcohol is put into vacuum oven, 100~120 DEG C at a temperature of, carry out vacuum drying 1 ~4h;
Step 2: the polymer diatomic alcohol after will be dry in step 1 pours into three-necked flask and adds diisocyanate, carries out Heating water bath stirring, the bath temperature that reaction system is arranged is 70~85 DEG C, and the time of stirring is 2~3h;
Step 3: being reduced to 60~70 DEG C for the bath temperature of reaction system, is added 2 into the resulting reaction solution of step 2, 2- dimethylolpropionic acid stirs 1.5~2.5h;
Step 4: being reduced to 45~55 DEG C for the bath temperature of reaction system, into step 3 resulting reaction solution in addition And agent, stir 20~45min;
Step 5: being reduced to 25~30 DEG C for the bath temperature of reaction system, is added and goes into the resulting reaction solution of step 4 Ionized water, 30~60min of high-speed stirred obtain no-solvent type aqueous polyurethane.
Further, in the step 1, the polymer diatomic alcohol is polytetrahydrofuran ether glycol, polycaprolactone, gathers One or more of mixtures of carbonate diol, polyadipate ethylene glycol, the molecular weight of polymer diatomic alcohol are 1000.
Further, in the step 2, the diisocyanate is isophorone diisocyanate, toluene diisocynate Ester, methyl diphenylene diisocyanate or polymethylene multi-phenenyl isocyanate.
Further, in the step 4, neutralizer is sodium hydroxide, ammonium hydroxide or triethylamine.
Further, described Step 2: in three, four, the revolving speed of stirring is 200 ~ 400 r/min;In step 5, stirring Revolving speed be 700 ~ 1200 r/min.
Further, polymer diatomic alcohol: diisocyanate: 2,2- dimethylolpropionic acids: neutralizer: deionized water Mass ratio is 23 ~ 38:10 ~ 26:1.5 ~ 4.0:0.6 ~ 2.2:100 ~ 140.
Embodiment 1
Firstly, 23g polytetrahydrofuran ether glycol is taken to be placed in a vacuum drying oven, 120 DEG C at a temperature of carry out vacuum drying 1 H is poured into three-necked flask and is added the progress heating water bath stirring of 10g toluene di-isocyanate(TDI), and setting bath temperature is 70 DEG C, with The revolving speed of 400r/min stirs 3h;Then, bath temperature is reduced to 60 DEG C, 2, the 2- dimethylolpropionic acid of 1.5g is added, with The revolving speed of 400r/min stirs 2.5h;Bath temperature is reduced to 45 DEG C again, 0.6g ammonium hydroxide is added, is stirred with the revolving speed of 400r/min Mix 45min;Bath temperature is reduced to 25 DEG C again, 100 g deionized waters are added, with the revolving speed high-speed stirred 30 of 1200 r/min Min obtains no-solvent type aqueous polyurethane.
Embodiment 2
Firstly, 38g polytetrahydrofuran ether glycol is taken to be placed in a vacuum drying oven, 100 DEG C at a temperature of carry out vacuum drying 4h, It pours into three-necked flask and adds 26g methyl diphenylene diisocyanate and carry out heating water bath stirring, setting bath temperature is 85 DEG C, 2h is stirred with the revolving speed of 200r/min;Then, bath temperature is down to 70 DEG C, 4.0 g 2,2- is added into reaction solution Dimethylolpropionic acid stirs 1.5h with the revolving speed of 200r/min;Bath temperature is reduced to 55 DEG C again, is added into reaction solution 2.2g triethylamine stirs 20min with the revolving speed of 200r/min;Finally, bath temperature is reduced to 30 DEG C again, to reaction solution plus Enter 140 g deionized waters, with the revolving speed high-speed stirred 60min of 700r/min, obtains no-solvent type aqueous polyurethane.
Embodiment 3
Firstly, 33g polytetrahydrofuran ether glycol is taken to be placed in a vacuum drying oven, 110 DEG C at a temperature of carry out vacuum drying 3h, It pouring into three-necked flask and adds 16g isophorone diisocyanate and carry out heating water bath stirring, setting bath temperature is 75 DEG C, 2.5h is stirred with the revolving speed of 300 r/min;Then, bath temperature is reduced to 65 DEG C, the 2 of 2.3g is added into reaction solution, 2- dimethylolpropionic acid stirs 2h with the revolving speed of 300r/min;Bath temperature is cooled to 50 DEG C again, is added into reaction solution 1.5g triethylamine stirs 30min with the revolving speed of 300r/min;Finally, bath temperature is reduced to 30 DEG C again, into reaction solution 125g deionized water is added, no-solvent type aqueous polyurethane is obtained with the revolving speed high-speed stirred 60min of 1000r/min.
Embodiment 4
Firstly, 30g polycaprolactone is taken to be placed in a vacuum drying oven, 110 DEG C at a temperature of carry out vacuum drying 2h, pour into three mouthfuls In flask and the progress heating water bath stirring of 15g isophorone diisocyanate is added, setting bath temperature is 75 DEG C, with 300r/ The revolving speed of min stirs 2.5 h;Then, bath temperature is reduced to 65 DEG C, 2, the 2- dihydroxy first of 2.5g is added into reaction solution Base butyric acid stirs 2h with the revolving speed of 300r/min;Bath temperature is cooled to 50 DEG C again, 0.7g hydrogen is added into reaction solution Sodium oxide molybdena stirs 30 min with the revolving speed of 300r/min;Finally, bath temperature is reduced to 30 DEG C again, add into reaction solution Enter 120g deionized water, with the revolving speed high-speed stirred 60min of 1000r/min, obtains no-solvent type aqueous polyurethane.
Embodiment 5
Firstly, 34g polycaprolactone is placed in a vacuum drying oven, after 110 DEG C of vacuum drying 2h, pours into three-necked flask and add Add 19g methyl diphenylene diisocyanate, setting bath temperature is 80 DEG C, stirs 2.5h with the revolving speed of 300r/min;Then, will Bath temperature is reduced to 65 DEG C, and 2, the 2- dimethylolpropionic acid of 2.7g is added into reaction solution, is stirred with the revolving speed of 300r/min Mix 2h;Bath temperature is reduced to 50 DEG C again, 1.8 g triethylamines are added into reaction solution, is stirred with the revolving speed of 300r/min 30min;Finally, bath temperature is reduced to 30 DEG C again, 130g deionized water is added, into reaction solution with 1000r/min's Revolving speed high-speed stirred 60min, obtains no-solvent type aqueous polyurethane.
Obtained no-solvent type aqueous polyurethane, the present inventor couple are prepared in order to test preparation method of the present invention Embodiment 1-5 prepares obtained product and carries out Mechanics Performance Testing, the tensile strength and elongation at break of material in embodiment It is surveyed using height spy's Weir (Dongguan) Co., Ltd AI-7000-NGD type servo material Multifunctional high-low temperature control testing machine Fixed, test result is as shown in table 1.As it can be seen from table 1 no-solvent type aqueous polyurethane, tensile strength prepared by the present invention In 40MPa or more, 1 ~ 2 times is improved compared to existing aqueous polyurethane.
The mechanical experimental results contrast table of aqueous polyurethane prepared by 1 present invention of table
Implementation project Tensile strength (MPa) Elongation at break (%)
Embodiment 1 40.309 531.31
Embodiment 2 43.442 577.297
Embodiment 3 44.814 580.746
Embodiment 4 42.678 591.657
Embodiment 5 40.008 566.704

Claims (7)

1. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile, which comprises the following steps:
Step 1: polymer diatomic alcohol is put into vacuum oven, 100~120 DEG C at a temperature of, carry out vacuum drying 1 ~4h;
Step 2: the polymer diatomic alcohol after will be dry in step 1 pours into three-necked flask and adds diisocyanate, carries out Heating water bath stirring, the bath temperature that reaction system is arranged is 70~85 DEG C, and the time of stirring is 2~3h;
Step 3: being reduced to 60~70 DEG C for the bath temperature of reaction system, is added 2 into the resulting reaction solution of step 2, 2- dimethylolpropionic acid stirs 1.5~2.5h;
Step 4: being reduced to 45~55 DEG C for the bath temperature of reaction system, into step 3 resulting reaction solution in addition And agent, stir 20~45min;
Step 5: being reduced to 25~30 DEG C for the bath temperature of reaction system, is added and goes into the resulting reaction solution of step 4 Ionized water, 30~60min of high-speed stirred obtain no-solvent type aqueous polyurethane.
2. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile according to claim 1, feature It is,
In the step 1, the polymer diatomic alcohol is polytetrahydrofuran ether glycol, polycaprolactone, polycarbonate glycol, gathers One or more of mixtures of adipate glycol, the molecular weight of polymer diatomic alcohol are 1000.
3. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile according to claim 1 or 2, special Sign is,
In the step 2, the diisocyanate is isophorone diisocyanate, toluene di-isocyanate(TDI), diphenyl methane Diisocyanate or polymethylene multi-phenenyl isocyanate.
4. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile according to claim 3, feature It is,
In the step 4, neutralizer is sodium hydroxide, ammonium hydroxide or triethylamine.
5. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile according to claim 4, feature It is,
It is described Step 2: in three, four, the revolving speed of stirring is 200 ~ 400 r/min;
In the step 5, the revolving speed of stirring is 700 ~ 1200 r/min.
6. a kind of preparation method of the no-solvent type aqueous polyurethane of high-tensile according to claim 5, feature It is,
Polymer diatomic alcohol: diisocyanate: 2,2- dimethylolpropionic acid: neutralizer: the mass ratio of deionized water be 23 ~ 38:10 ~ 26:1.5 ~ 4.0:0.6 ~ 2.2:100 ~ 140.
7. the aqueous poly- ammonia of the no-solvent type for the high-tensile that preparation method as claimed in any one of claims 1 to 6 is prepared Ester.
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Cited By (3)

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CN110862509A (en) * 2019-11-29 2020-03-06 山东天庆科技发展有限公司 Water-based solvent-free polyurethane resin and preparation method thereof
CN111909351A (en) * 2020-06-23 2020-11-10 明新孟诺卡(浙江)新材料有限公司 Synthetic method and application of waterborne polyurethane for microfiber impregnation
CN118029131A (en) * 2024-04-12 2024-05-14 四川大学 Modified wool fiber, preparation method, composite water-based resin and preparation method thereof

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