CN107880247A - A kind of self-crosslinking modified aqueous polyurethane resin and preparation method thereof - Google Patents

A kind of self-crosslinking modified aqueous polyurethane resin and preparation method thereof Download PDF

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Publication number
CN107880247A
CN107880247A CN201711166999.7A CN201711166999A CN107880247A CN 107880247 A CN107880247 A CN 107880247A CN 201711166999 A CN201711166999 A CN 201711166999A CN 107880247 A CN107880247 A CN 107880247A
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polyurethane resin
self
aqueous polyurethane
modified aqueous
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刘巧
黄军波
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Heshan River Ben Polyfat Chemical Co Ltd
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Heshan River Ben Polyfat Chemical Co Ltd
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/44—Polycarbonates
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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
    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates 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
    • C08G18/753—Polyisocyanates 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
    • C08G18/755—Polyisocyanates 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：20~40 parts of polyisocyanates, 100~150 parts of polyalcohol, 3~5 parts of organosilicon, the first 5~10 parts of chain extender, 10~15 parts of triethylamine, the second 3~6 parts of chain extender, 5~10 parts of hydroxyl vinyl monomer, 50~150 parts of vinyl monomer, 0.05~0.1 part of organic bismuth catalyst, 400~600 parts of water.The self-crosslinking modified aqueous polyurethane resin of the present invention, it can be used in stereoplasm stamp, its coating flexibility is good, and being not required to curing agent addition also has the features such as fabulous solid color, excellent wash durability, the requirement of printing in textiles is fully achieved in the softness of its drying and forming-film, it is stiff to improve conventional polyurethanes feel simultaneously, the defects of washing fastness difference, without any solvent in building-up process, directly using vinyl monomer as solvent, trigger crosslinking after emulsification.The technique for simplifying solvent removed by vacuum, shortens the production time, fully meets the requirement of stereoplasm stamp.

Description

A kind of self-crosslinking modified aqueous polyurethane resin and preparation method thereof
Technical field
The invention belongs to high molecular polymer field, and in particular to a kind of self-crosslinking modified aqueous polyurethane resin and its system Preparation Method.
Background technology
Stereoplasm stamp typically makees adhesive to produce using acrylic emulsion, and it, which must add curing agent, just has preferably Fastness, and chemical fibre class cloth fastness is short of.
The content of the invention
A kind of the defects of it is an object of the invention to overcome above-mentioned prior art, there is provided self-crosslinking available for stereoplasm stamp Modified aqueous polyurethane resin and preparation method thereof, for overcoming in the prior art, polyurethane film-forming sense of touch is stiff, water-wash resistance The defects of difference, necessary outer addition curing agent, reach production requirement without adding curing agent can.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Polyisocyanates 20~ 40 parts, 100~150 parts of polyalcohol, 3~5 parts of organosilicon, the first 5~10 parts of chain extender, 10~15 parts of triethylamine, the second chain extension 3~6 parts of agent, 5~10 parts of hydroxyl vinyl monomer, 50~150 parts of vinyl monomer, 0.05~0.1 part of organic bismuth catalyst, 400~600 parts of water.
Preferably, it is different to be selected from toluene di-isocyanate(TDI), IPDI, diphenyl methane two for polyisocyanates Cyanate, hexamethylene diisocyanate, XDI, naphthalene -1,5- diisocyanate, polymethylene polyphenyl Isocyanates, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate and the isocyanide of dicyclohexyl methyl hydride two One or more in acid esters.
Preferably, polyalcohol is selected from polycaprolactone polyol, polycarbonate polyol, PolyTHF ethoxylated polyhydric alcohol, poly- In ethylene oxide polyol, polyoxypropylene polyol, end hydroxy butadiene, polysiloxane polyhydric alcohol and polyesterether polyols One or more.Combination polyalcohol is to reach optimum balance between soft and hydrolysis.
Preferably, polyalcohol is selected from caprolactone dihydric alcohol, PCDL, PTMG dihydric alcohol, polycyclic One or more in oxidative ethane dihydric alcohol, polypropylene oxide glycol, end hydroxy butadiene and polysiloxane binary alcohol.
Preferably, polyisocyanates group is with the ratio between molal quantity of oh group in the polyalcohol in polyisocyanates 0.97~0.98.
Preferably, the first chain extender is selected from dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxymethyl One or more in octanoic acid.
Preferably, the second chain extender be selected from ethylene glycol, diglycol, BDO, 2,3-butanediol, 1,6- oneself One or more in glycol, neopentyl glycol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane and hydroxymethyl-cyclohexane.
Preferably, vinyl monomer is selected from EHMA, Isooctyl acrylate monomer, butyl acrylate, acrylic acid Ethyl ester, acrylic acid, acetoacetoxyethyl methacrylate (AAEM), DAAM (DAAM), N- methylols third One or more in acrylamide (NMA), GMA (GMA).Vinyl monomer act as adjustment instead The viscosity of solution is answered, adjusts film forming feel.The addition of vinyl monomer can need to take the circumstances into consideration to add according to reaction.
Preferably, hydroxyl vinyl monomer is selected from hydroxypropyl acrylate or hydroxyl ethyl ester.Hydroxyl vinyl monomer is by polyurethane Molecule chains the key of acrylic molecules chain, and addition is to synthesize the key whether being demulsified.
A kind of method for preparing the self-crosslinking modified aqueous polyurethane resin, comprises the following steps：
(1) polyalcohol and polyisocyanates are reacted into 2~3h at 85~95 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, react 1 at 75~85 DEG C~ 3h；
(3) organic bismuth catalyst and hydroxyl vinyl monomer are added, 2~3h is reacted at 65~75 DEG C；
(4) vinyl monomer is added, is cooled to 35~45 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2~3h is reacted at 85~95 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Preferably, organic bismuth catalyst is selected from Coscat83, organo-bismuth 1610, organo-bismuth 2010, organo-bismuth 2810, organic One or more in bismuth 2808.
The invention also discloses a kind of purposes of waterborne polyurethane resin as described above in stereoplasm stamp.The purposes For the waterborne polyurethane resin through thickening, soak, after defoaming treatment, can be directly coated with.The thickening, soak, at defoaming Step is managed to carry out using usual way in the prior art.
The self-crosslinking modified aqueous polyurethane resin of the present invention, can be used in stereoplasm stamp, its coating flexibility is good, is not required to Curing agent addition also has the features such as fabulous solid color, excellent wash durability.
Printing in textiles is fully achieved in the self-crosslinking modified aqueous polyurethane resin of the present invention, the softness of its drying and forming-film It is required that while to improve conventional polyurethanes feel stiff, the defects of washing fastness difference, without any solvent in building-up process, Directly using vinyl monomer as solvent, trigger crosslinking after emulsification.The technique for simplifying solvent removed by vacuum, when shortening production Between, fully meet the requirement of stereoplasm stamp.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the specific embodiment party of the present invention Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Toluene di-isocyanate(TDI) 30 parts, 125 parts of PCDL, 4 parts of organosilicon, 7 parts of the first chain extender (dihydromethyl propionic acid), 12 parts of triethylamine, the 4 parts of two chain extenders (ethylene glycol), 0.05 part of organic bismuth catalyst, 7 parts of hydroxyl vinyl monomer (hydroxypropyl acrylate), vinyl monomer 100 parts of (EHMA), 500 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 2.5h at 90 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 2h at 80 DEG C；
(3) organic bismuth catalyst (Coscat83) and hydroxyl vinyl monomer are added, reacts 2.5h at 70 DEG C；
(4) vinyl monomer is added, is cooled to 40 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2.5h is reacted at 90 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Embodiment 2
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：The isocyanide of isophorone two 20 parts of acid esters, 100 parts of PTMG dihydric alcohol, 3 parts of organosilicon, 5 parts of the first chain extender (dimethylolpropionic acid), triethylamine 10 parts, 3 parts of the second chain extender (BDO), 5 parts of hydroxyl vinyl monomer (hydroxyl ethyl ester), vinyl monomer (acrylic acid Butyl ester) 50 parts, 0.1 part of organic bismuth catalyst, 400 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 2h at 85 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 1h at 75 DEG C；
(3) organic bismuth catalyst (organo-bismuth 1610) and hydroxyl vinyl monomer are added, reacts 2h at 65 DEG C；
(4) vinyl monomer is added, is cooled to 35 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2h is reacted at 85 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Embodiment 3
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：The isocyanic acids of naphthalene -1,5- two 40 parts of ester, 150 parts of polyethylene oxide glycol, 5 parts of organosilicon, 10 parts of the first chain extender (dihydroxymethyl valeric acid), triethylamine 15 Part, 6 parts of the second chain extender (1,6- hexylene glycol), 10 parts of hydroxyl vinyl monomer (hydroxyl ethyl ester), vinyl monomer (AAEM) 150 Part, 0.07 part of organic bismuth catalyst, 600 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 3h at 95 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 3h at 85 DEG C；
(3) organic bismuth catalyst (organo-bismuth 2010) and hydroxyl vinyl monomer are added, reacts 3h at 75 DEG C；
(4) vinyl monomer is added, is cooled to 45 DEG C, triethylamine is added and neutralizes；
(5) water is added, 3h is reacted at 95 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Embodiment 4
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Methylcyclohexyl two is different 30 parts of cyanate, 125 parts of end hydroxy butadiene, 4 parts of organosilicon, 7 parts of the first chain extender (dihydromethyl propionic acid), triethylamine 12 Part, 4 parts of the second chain extender (ethylene glycol), 7 parts of hydroxyl vinyl monomer (hydroxyl ethyl ester), 100 parts of vinyl monomer (DAAM), have 0.06 part of machine bismuth catalyst, 500 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 2.5h at 90 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 2h at 80 DEG C；
(3) organic bismuth catalyst (organo-bismuth 2810) and hydroxyl vinyl monomer are added, reacts 2.5h at 70 DEG C；
(4) vinyl monomer is added, is cooled to 40 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2.5h is reacted at 90 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Embodiment 5
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Phenylenedimethylidyne two is different 20 parts of cyanate, 100 parts of polysiloxane binary alcohol, 3 parts of organosilicon, 5 parts of the first chain extender (dimethylolpropionic acid), triethylamine 10 Part, 3 parts of the second chain extender (BDO), 5 parts of hydroxyl vinyl monomer (hydroxyl ethyl ester), 50 parts of vinyl monomer (NMA), 0.08 part of organic bismuth catalyst, 400 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 2h at 85 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 1h at 75 DEG C；
(3) organic bismuth catalyst (organo-bismuth 2808) and hydroxyl vinyl monomer are added, reacts 2h at 65 DEG C；
(4) vinyl monomer is added, is cooled to 35 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2h is reacted at 85 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
Embodiment 6
A kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Dicyclohexyl methyl hydride two 40 parts of isocyanates, 150 parts of polypropylene oxide glycol, 5 parts of organosilicon, 10 parts of the first chain extender (dihydroxymethyl valeric acid), three 15 parts of ethamine, 6 parts of the second chain extender (1,6- hexylene glycol), 10 parts of hydroxyl vinyl monomer (hydroxypropyl acrylate), vinyl monomer (GMA) 150 parts, 0.1 part of organic bismuth catalyst, 600 parts of water.
Above-mentioned self-crosslinking modified aqueous polyurethane resin is made by following steps：
(1) polyalcohol and polyisocyanates are reacted into 3h at 95 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, reacts 3h at 85 DEG C；
(3) organic bismuth catalyst (organo-bismuth 2010) and hydroxyl vinyl monomer are added, reacts 3h at 75 DEG C；
(4) vinyl monomer is added, is cooled to 45 DEG C, triethylamine is added and neutralizes；
(5) water is added, 3h is reacted at 95 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.

Claims (10)

1. a kind of self-crosslinking modified aqueous polyurethane resin, include the raw material components of following parts by weight：Polyisocyanates 20~40 Part, 100~150 parts of polyalcohol, 3~5 parts of organosilicon, the first 5~10 parts of chain extender, 10~15 parts of triethylamine, the second chain extender 3 ~6 parts, 5~10 parts of hydroxyl vinyl monomer, 50~150 parts of vinyl monomer, 0.05~0.1 part of organic bismuth catalyst, water 400~600 parts.
2. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The polyisocyanates choosing From toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, hexamethylene diisocyanate, benzene Dimethylene diisocyanate, naphthalene -1,5- diisocyanate, polymethylene multi-phenenyl isocyanate, tetramethylxylene One or more in diisocyanate, Methylcyclohexyl diisocyanate and dicyclohexyl methyl hydride diisocyanate.
3. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The polyalcohol is selected from poly- Caprolactone polyol, polycarbonate polyol, PolyTHF ethoxylated polyhydric alcohol, polyethylene oxide polyol, PPOX are more One or more in first alcohol, end hydroxy butadiene, polysiloxane polyhydric alcohol and polyesterether polyols.
4. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The polyalcohol is selected from poly- Caprolactone dihydric alcohol, PCDL, PTMG dihydric alcohol, polyethylene oxide glycol, PPOX two One or more in first alcohol, end hydroxy butadiene and polysiloxane binary alcohol.
5. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：In the polyisocyanates The ratio between molal quantity of oh group is 0.97~0.98 in polyisocyanates group and the polyalcohol.
6. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The first chain extender choosing One or more from dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxymethyl octanoic acid.
7. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The second chain extender choosing From ethylene glycol, diglycol, 1,4- butanediols, 2,3- butanediols, 1,6-HD, neopentyl glycol, diethylene glycol (DEG), glycerine, One or more in sorbierite, trimethylolpropane and hydroxymethyl-cyclohexane.
8. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The vinyl monomer choosing From EHMA, Isooctyl acrylate monomer, butyl acrylate, ethyl acrylate, acrylic acid, methacrylic acid acetyl second One kind or several in acyloxy ethyl ester, DAAM, N hydroxymethyl acrylamide, GMA Kind.
9. self-crosslinking modified aqueous polyurethane resin according to claim 1, it is characterised in that：The hydroxyl vinyl Monomer is selected from hydroxypropyl acrylate or hydroxyl ethyl ester.
10. a kind of method for preparing the self-crosslinking modified aqueous polyurethane resin described in claim any one of 1-9, its feature exist In comprising the following steps：
(1) polyalcohol and polyisocyanates are reacted into 2~3h at 85~95 DEG C；
(2) the first chain extender and the second chain extender are added, while adds vinyl monomer, 1~3h is reacted at 75~85 DEG C；
(3) organic bismuth catalyst and hydroxyl vinyl monomer are added, 2~3h is reacted at 65~75 DEG C；
(4) vinyl monomer is added, is cooled to 35~45 DEG C, triethylamine is added and neutralizes；
(5) water is added, 2~3h is reacted at 85~95 DEG C, obtains self-crosslinking modified aqueous polyurethane resin.
CN201711166999.7A 2017-11-21 2017-11-21 A kind of self-crosslinking modified aqueous polyurethane resin and preparation method thereof Withdrawn CN107880247A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108867113A (en) * 2018-06-06 2018-11-23 苏州印丝特纺织数码科技有限公司 A kind of pigment printing adhesive and preparation method thereof
CN109503808A (en) * 2018-10-31 2019-03-22 上纬新材料科技股份有限公司 Low viscous high-strength polyurethane acrylic resin of one kind and preparation method thereof
CN112341594A (en) * 2020-10-30 2021-02-09 西安工程大学 Preparation method of waterborne polyurethane color fixing agent
WO2023220923A1 (en) * 2022-05-17 2023-11-23 Dow Global Technologies Llc Polyurethane compositions, composite materials prepared with same and preparation methods thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108867113A (en) * 2018-06-06 2018-11-23 苏州印丝特纺织数码科技有限公司 A kind of pigment printing adhesive and preparation method thereof
CN109503808A (en) * 2018-10-31 2019-03-22 上纬新材料科技股份有限公司 Low viscous high-strength polyurethane acrylic resin of one kind and preparation method thereof
CN112341594A (en) * 2020-10-30 2021-02-09 西安工程大学 Preparation method of waterborne polyurethane color fixing agent
WO2023220923A1 (en) * 2022-05-17 2023-11-23 Dow Global Technologies Llc Polyurethane compositions, composite materials prepared with same and preparation methods thereof

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