CN105968309B - A kind of waterborne polyurethane resin and preparation method thereof for synthetic leather fabric - Google Patents
A kind of waterborne polyurethane resin and preparation method thereof for synthetic leather fabric Download PDFInfo
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- CN105968309B CN105968309B CN201610494902.4A CN201610494902A CN105968309B CN 105968309 B CN105968309 B CN 105968309B CN 201610494902 A CN201610494902 A CN 201610494902A CN 105968309 B CN105968309 B CN 105968309B
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- chain extender
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- diisocyanate
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- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/44—Polycarbonates
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- 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
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
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- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of waterborne polyurethane resin and preparation method thereof for synthetic leather fabric, including following raw material components and parts by weight：120~150 parts of polyalcohol；20~35 parts of polyisocyanates；First 3~6 parts of chain extender；Second 1~8 part of chain extender；1~8 part of third chain extender；2~6 parts of salt forming agent, wherein the polyalcohol includes polycarbonate polyol and polysiloxane polyhydric alcohol, and the weight ratio of the polycarbonate polyol and the polysiloxane polyhydric alcohol is (9-13):(0.1-0.4).The synthetic leather fabric that the waterborne polyurethane resin that the present invention obtains is prepared into is not only soft without viscous, but also has many advantages, such as excellent hydrolytic resistance, folding resistance.
Description
Technical field
The present invention relates to high molecular polymer fields, specifically disclose a kind of aqueous polyurethane tree for synthetic leather fabric
Fat and preparation method thereof.
Background technology
Waterborne polyurethane resin is to be not necessarily to organic solvent, and product system in process using water as decentralized medium
In do not contain toxic NCO group, avoid the pollution to environment and the health hazard to operating personnel.Waterborne polyurethane resin
It is widely applied to synthetic leather fabric field, Waterborne synthetic leather fabric has asepsis environment-protecting without organic solvents such as benzene homologues, DMF
The advantages of, liked by more and more consumers.But it due to technically being limited using waterborne polyurethane resin by synthetic leather, leads
Waterborne synthetic leather development is caused to be restricted, especially on soft synthetic leather fabric, one side feel does not have solvent shell fabric plentiful, modeling
Glue sense is serious, and on the other hand, if the feel of synthetic leather is done soft, often synthetic leather surface will appear tacky problem.Therefore,
There is an urgent need for work out a kind of waterborne polyurethane resin to solve the problems, such as feel existing for synthetic leather fabric.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of aqueous polyurethane for synthetic leather fabric is provided
Resin and preparation method thereof, the synthetic leather fabric prepared by the waterborne polyurethane resin is not only soft without viscous, but also with excellent
Hydrolytic resistance, folding resistance.
In order to realize object above and other purposes, the present invention including following technical scheme by realizing：A kind of water
Property polyurethane resin, including following raw material components and parts by weight：
Preferably, the polyalcohol is 130~140 parts.
Preferably, the polyisocyanates is 25~30 parts.
Preferably, first chain extender is 4~5 parts.
Preferably, second chain extender is 4~7 parts.
Preferably, the third chain extender is 4~7 parts.
Preferably, the salt forming agent is 3~5 parts.
Preferably, the polyalcohol includes polycarbonate polyol and polysiloxane polyhydric alcohol, the polycarbonate polyol
The weight ratio of alcohol and the polysiloxane polyhydric alcohol is (9-13):(0.1-0.4).
It is highly preferred that the polyalcohol further includes polyoxypropylene polyol and/or polytetrahydrofuran polyol.
It is highly preferred that the polycarbonate polyol is by caprolactone and 1,6- hexylene glycols polymerisation and obtain, it is described
The molecular weight of polycarbonate polyol is 1800-2100.
Preferably, the polyisocyanates is selected from toluene di-isocyanate(TDI), isophorone diisocyanate, 4,4-, bis- hexamethylenes
Dicyclohexylmethane diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate,
Naphthalene -1,5- diisocyanate, polymethylene multi-phenenyl isocyanate, tetramethylxylylene diisocyanate, methyl cyclohexane
Any one or more in group diisocyanate and dicyclohexyl methyl hydride diisocyanate.
Preferably, first chain extender is selected from dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxy
It is one or more in methyloctanoic acid.
Preferably, second chain extender is selected from ethylene glycol, diglycol, 1,4-butanediol, 2,3-butanediol, 1,
One kind or more in 6- hexylene glycols, neopentyl glycol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane and hydroxymethyl-cyclohexane
Kind.
Preferably, the third chain extender is selected from ethylenediamine, isophorone diamine, 1,6- hexamethylene diamines, 1,3- hexamethylene diformazans
Any one or more in amine and m-xylene diamine.
Preferably, the salt forming agent is triethylamine.
The present invention discloses a kind of method preparing waterborne polyurethane resin as described above, includes the following steps：By institute
It states polyalcohol and the polyisocyanates and reacts 2~3h at 85~95 DEG C；Add first chain extender and described second
Chain extender reacts 5~8h at 75~85 DEG C；It is cooled to 0~5 DEG C and the salt forming agent neutralization is added；Described is added after adding water
Three chain extenders, vacuum distillation obtain waterborne polyurethane resin.
Preferably, acetone is added while first chain extender and second chain extender is added.
The viscosity for acting as adjustment reaction solution of acetone.The additive amount of acetone can need to take the circumstances into consideration to add according to reaction.Institute
It states acetone and is distilled removing in the vacuum distillation stage.
Invention additionally discloses a kind of waterborne polyurethane resin as described above or method described above prepare it is aqueous
Purposes of the polyurethane resin in synthetic leather fabric.
In conclusion the present invention provides a kind of waterborne polyurethane resin and preparation method thereof for synthetic leather fabric,
It has the beneficial effect that：
The present invention is added polycarbonate polyol and polysiloxane polyhydric alcohol in aqueous polyurethane preparation process, and poly- carbon
Acid esters polyalcohol is by caprolactone and 1, and 6- hexylene glycols are reacted and obtained, since caprolactone has lower glass transition temperature,
Itself is very soft, has great extensibility so that not only feel is soft for the synthetic leather fabric prepared by acquisition aqueous polyurethane
It is soft, and there is excellent hydrolytic resistance, room temperature and low temperature flexible resistance, it is also very excellent in terms of wear-resisting, solvent resistance；
Polysiloxane polyhydric alcohol can give the synthetic leather prepared by waterborne polyurethane resin to bring softness, smooth feel, simultaneously
Avoid the problem that the adhesion of Waterborne synthetic leather fabric；The synthetic leather fabric prepared by the waterborne polyurethane resin that obtains it is not only soft and
It does not glue, and there is excellent hydrolytic resistance, Martindale abrasion resistance energy and solvent resistance.
Specific implementation mode
With reference to embodiment, the present invention is further explained.It should be understood that embodiment is merely to illustrate the present invention, and it is unrestricted
The scope of the present invention.
Embodiment 1
It is small that 130g polycarbonate polyols (molecular weight 2000) and 3g polysiloxane polyhydric alcohols are dehydrated at 100 DEG C to one
When, 50 DEG C are then cooled to, the toluene di-isocyanate(TDI) of 23g is added, is warming up to 90 DEG C of insulation reactions 2 hours, is measured within two hours
NCO content is cooled to 50 DEG C after reaching theoretical value, and the dihydromethyl propionic acid of 4.68g and the 1,4-butanediol of 1.8g is added and lacks
It measures acetone and adjusts viscosity, be warming up to 80 DEG C and react 6 hours, reaction terminates to measure NCO content, is then cooled to 5 DEG C, is added
The triethylamine of 3.53g is neutralized, and after neutralizing 30 minutes, is added deionized water under high speed shear, disperses 2 minutes, then slowly
The ethylenediamine of the diluted 2g of addition ice water is evaporated under reduced pressure the acetone in removing system to get to sample 1.
Embodiment 2
By 110g polycarbonate polyols (molecular weight 2000), 32g Polyoxypropylene diols (molecular weight 2000)
It is dehydrated one hour at 110 DEG C with 2g polysiloxane binary alcohols, is then cooled to 50 DEG C, the isophorone diisocyanate of 32g is added
Ester, is warming up to 90 DEG C of insulation reactions 3 hours, measures NCO content within two hours, is cooled to 50 DEG C after reaching theoretical value, 3.2g is added
Dihydromethyl propionic acid and 6.2g 1,4-butanediol and a small amount of acetone adjust viscosity, be warming up to 80 DEG C react 6 hours, reaction knot
Beam measures NCO content, is then cooled to 5 DEG C, and the triethylamine that 2.41g is added is neutralized, after neutralizing 30 minutes, under high speed shear
Deionized water is added, disperses 2 minutes, is then slowly added into the isophorone diamine with the diluted 4g of ice water, vacuum distillation removes
Acetone in system is to get to sample 2.
Embodiment 3
By 90g polycarbonate polyols (molecular weight 2000), 40g polytetrahydrofuran polyols (molecular weight 2000) and
2g polysiloxane binary alcohols are dehydrated one hour at 105 DEG C, are then cooled to 50 DEG C, and the toluene di-isocyanate(TDI) of 32g is added, heating
To 90 DEG C of insulation reactions 3 hours, measures NCO content within two hours, be cooled to 50 DEG C after reaching theoretical value, the dihydroxy of 5.86g is added
The diglycol and a small amount of acetone of methylpropanoic acid and 3g adjust viscosity, are warming up to 80 DEG C and react 6 hours, and reaction terminates to measure
Then NCO content is cooled to 5 DEG C, the triethylamine that 4.41g is added is neutralized, and is added and goes after neutralizing 30 minutes, under high speed shear
Ionized water disperses 2 minutes, is then slowly added into the ethylenediamine with the diluted 2.1g of ice water, third be evaporated under reduced pressure in removing system
Ketone is to get to sample 3.
Embodiment 4
By 120g polycarbonate polyols (molecular weight 2000), 18g polytetrahydrofuran polyols (molecular weight 3000)
It is dehydrated one hour at 105 DEG C with 2g polysiloxane binary alcohols, is then cooled to 50 DEG C, the isophorone diisocyanate of 35g is added
Ester, is warming up to 90 DEG C of insulation reactions 3 hours, measures NCO content within two hours, is cooled to 50 DEG C after reaching theoretical value, 5.33g is added
Dihydromethyl propionic acid and 2g 1,4-butanediol and a small amount of acetone adjust viscosity, be warming up to 80 DEG C react 6 hours, reaction terminates
NCO content is measured, is then cooled to 5 DEG C, the triethylamine that 4.01g is added is neutralized, and after neutralizing 30 minutes, is added under high speed shear
Enter deionized water, disperse 2 minutes, be then slowly added into the ethylenediamine with the diluted 1.2g of ice water, is evaporated under reduced pressure in removing system
Acetone to get to sample 4.
Comparative example 1
By 120g polycarbonate polyols (molecular weight 2000) and 18g polytetrahydrofuran polyols (molecular weight 3000)
It is dehydrated one hour at 105 DEG C, is then cooled to 50 DEG C, the isophorone diisocyanate of 35g is added, it is anti-to be warming up to 90 DEG C of heat preservations
It answers 3 hours, measures NCO content within two hours, be cooled to 50 DEG C after reaching theoretical value, the dihydromethyl propionic acid and 2g of 5.33g is added
1,4-butanediol and a small amount of acetone adjust viscosity, be warming up to 80 DEG C react 6 hours, reaction terminate measure NCO content, then drop
To 5 DEG C, the triethylamine that 4.01g is added is neutralized temperature, and after neutralizing 30 minutes, deionized water is added under high speed shear, disperses 2 points
Clock, is then slowly added into the ethylenediamine with the diluted 1.2g of ice water, is evaporated under reduced pressure the acetone in removing system to get to sample 5.
Test result
(1) existed using the waterborne polyurethane resin obtained in four glasss of test embodiment of the present invention 1~4 of painting and comparative example 1
Viscosity at 25 DEG C is respectively：75S,67S,70S,72S,84S.
(2) aqueous polyurethane for selling obtained in above-described embodiment 5 aqueous polyurethane samples and two kinds of markets
Synthetic leather fabric is made in resin with identical technique, then carries out pliability, viscosity, alcohol resistance and water resistance test.
Wherein, pliability：Very soft is 5 grades, and 4 grades soft, relatively soft is 3 grades, and harder is 2 grades, and hard is 1 grade；
Viscosity：Very viscous is 5 grades, glues 4 grades, and it is 3 grades relatively to glue, and it is 2 grades less to glue, and does not glue 1 grade.
The performance of synthetic leather fabric made of the aqueous polyurethane that table 1 is sold embodiment 1-4, comparative example 1 and market is surveyed
Test result
Table 1 is the property of synthetic leather fabric made of the waterborne polyurethane resin of embodiment 1 to 4, comparative example 1 and market sale
It can test result.As seen from Table 1, synthetic leather made of waterborne polyurethane resin is obtained embodiment 1 to 4 and comparative example 1
The better softness of fabric, also having to viscosity performance greatly improves, the viscosity of the synthetic leather fabric of embodiment 1 to 4 better than pair
Ratio 1 illustrates that the viscosity performance that polysiloxane polyhydric alcohol improves synthetic leather is added；And by embodiment 1 to 4 and comparative example
1 obtains synthetic leather fabric made of aqueous polyurethane is not less than by market in room temperature, low temperature folding resistance and hydrolytic resistance
Synthetic leather fabric made of aqueous polyurethane in sale.So obtaining synthetic leather made of aqueous polyurethane embodiment 1 to 4
Fabric haveing excellent performance in terms of pliability, viscosity, hydrolytic resistance and folding resistance, can especially do in terms of pliability, viscosity
To soft without gluing, the product quality of synthetic leather fabric is substantially improved.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical scheme of the present invention
It is interior.
Claims (5)
1. a kind of waterborne polyurethane resin for synthetic leather fabric, it is characterised in that：Including following raw material components and parts by weight：
Wherein, the polyalcohol includes polycarbonate polyol and polysiloxane polyhydric alcohol, and the polycarbonate polyol passes through
Caprolactone and 1,6- hexylene glycols polymerisation and obtain, the molecular weight of the polycarbonate polyol is 1800-2100, described poly-
The weight ratio of carbonate polyol and the polysiloxane polyhydric alcohol is (9-13):(0.1-0.4), the first chain extender choosing
From one or more in dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxymethyl octanoic acid, described second
Chain extender is selected from ethylene glycol, diglycol, 1,4- butanediols, 2,3- butanediols, 1,6-HD, neopentyl glycol, two sweet
One or more in alcohol, glycerine, sorbierite, trimethylolpropane and hydroxymethyl-cyclohexane, the third chain extender is selected from
Any one or more in ethylenediamine, isophorone diamine, 1,6- hexamethylene diamines, 1,3- hexamethylenes dimethylamine and m-xylene diamine.
2. waterborne polyurethane resin as described in claim 1, it is characterised in that：The polyalcohol further includes that polypropylene oxide is polynary
Alcohol and/or polytetrahydrofuran polyol.
3. anion aqueous polyurethane resin as described in claim 1, it is characterised in that：The polyisocyanates is selected from toluene
Diisocyanate, isophorone diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanates, diphenylmethane diisocyanate
Ester, hexamethylene diisocyanate, benzene dimethylene diisocyanate, naphthalene -1,5- diisocyanate, polymethylene polyphenyl isocyanide
Acid esters, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate and dicyclohexyl methyl hydride diisocyanate
In any one or more.
4. a kind of method preparing the waterborne polyurethane resin as described in claims 1 to 3 is any, it is characterised in that：Including with
Lower step：The polyalcohol and the polyisocyanates are reacted into 2~3h at 85~95 DEG C；Add first chain extender
5~8h is reacted at 75~85 DEG C with second chain extender；It is cooled to 0~5 DEG C and the salt forming agent neutralization is added；Add after water again
The third chain extender is added, is evaporated under reduced pressure, obtains waterborne polyurethane resin.
5. the preparation method of waterborne polyurethane resin as claimed in claim 4, it is characterised in that：First chain extender is added
Acetone is added while with second chain extender.
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| CN107141434B (en) * | 2017-06-08 | 2019-12-27 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof |
| CN111655761A (en) * | 2017-11-17 | 2020-09-11 | 派珀接入公司 | Alcohol resistant siliconized polycarbonate polyurethane and medical devices incorporating the same |
| CN108456296A (en) * | 2017-12-29 | 2018-08-28 | 合肥科天水性科技有限责任公司 | A kind of waterborne polyurethane resin and preparation method thereof for clothing leather |
| CN110041485A (en) * | 2019-04-02 | 2019-07-23 | 浙江诚迅新材料有限公司 | A kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application method |
| CN111303370B (en) * | 2020-04-13 | 2022-06-21 | 齐鲁工业大学 | Method for preparing waterborne polyurethane by adopting post-chain extender |
| CN114274642B (en) * | 2021-12-24 | 2024-05-31 | 无锡翔隆高分子面料有限公司 | Thermoplastic polyurethane fabric and preparation method and application thereof |
| CN115710339A (en) * | 2022-11-10 | 2023-02-24 | 江苏休伦新材料有限公司 | Bio-based waterborne polyurethane for clothing leather surface layer and preparation method thereof |
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