CN106632951A - Maleic anhydride modified urethane acrylate waterborne resin and preparation method - Google Patents
Maleic anhydride modified urethane acrylate waterborne resin and preparation method Download PDFInfo
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- CN106632951A CN106632951A CN201611004627.XA CN201611004627A CN106632951A CN 106632951 A CN106632951 A CN 106632951A CN 201611004627 A CN201611004627 A CN 201611004627A CN 106632951 A CN106632951 A CN 106632951A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
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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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The invention discloses maleic anhydride modified urethane acrylate waterborne resin. The maleic anhydride modified urethane acrylate waterborne resin is prepared from, by weight, 1-2 parts of maleic anhydride, 1-3 parts of trimethylpropane, 22-32 parts of diisocyanate, 42-53 parts of polyether glycol, 0.5-2 parts of ethylene glycol, 7-10 parts of methacrylate, 1-2.0 parts of triethylamine and 9-13 parts of deionized water. A catalyst accounts for 0.02-0.05% of the total mass of the raw materials. A polymerization inhibitor accounts for 0.04-0.06% of the total mass of the raw materials. A waterborne diluent monomer is used for regulating the system viscosity to 10-20% of the total mass of the raw materials. The maleic anhydride modified urethane acrylate waterborne resin contains zero organic volatile substance (VOC), is environmentally friendly and can be widely applied to water-based furniture coatings.
Description
Technical field
The present invention relates to a kind of modified urethane acrylate waterborne ultraviolet curing resin, can be widely applied to aqueous furniture and applies
The fields such as material, printing-ink.
Background technology
With the attention of Environmental pollution problem, coating industry correlation mandatory standard is put into effect in succession, to limit coating row
Industry harmful organic volatile compounds（VOC）Discharge.Meanwhile, country actively encourages development green environmental friendly coatingses, such as water paint, UV to apply
Material etc., to substitute harmful organic volatile compounds（VOC）The larger traditional solvent-borne coating of discharge capacity.Wherein, UV-curable water-borne
Coating is a kind of coating for being caused by light trigger and producing chemical crosslinking film forming, compensate for single-component water-based coating intensity not enough
Shortcoming.The cis-butenedioic anhydride modified urethane acrylate water-base resin of invention, is a kind of ultraviolet solidified aqueous coating.
It is prepared by a kind of Yu Xueya et al. aqueous polyurethane acrylate resins disclosed in Chinese patent CN 101475679A
Methods and applications.Liu Xiaoxuan et al. discloses ultraviolet light solidfication water polyurethane propylene in Chinese patent CN 103214652A
Acid esters vacuum coating bottom coating resin.Above patent is to introduce carboxyl with amine into salt by 2,2- dihydromethyl propionic acids, realizes water
Property.2,2- dihydromethyl propionic acid prices it is higher and in reaction system compared with indissoluble solution.This patent introduces carboxylic by cis-butenedioic anhydride open loop
Base, realizes Water-borne modification, and dissolubility is preferably and cis-butenedioic anhydride is the industrial chemicals on basis in reaction system for it, and its abundance has
Preferable price advantage.
A kind of cis-butenedioic anhydride modified urethane acrylate water-base resin of invention, as the main film forming matter of coating
Matter, can apply to different aqueous coating formulations；Its cost performance is higher, better performances, can make up single-component water-based coating
The not enough shortcoming of intensity, and using the curing mode of ultraviolet light irradiation, there is fast curing rate, cleaning, environmental protection.
The content of the invention
The present invention is intended to provide a kind of cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that by following portions by weight
Composition：
Cis-butenedioic anhydride 1 ~ 2；
Trimethylolpropane 1 ~ 3；
Diisocyanate 22 ~ 32；
Polyether Glycols 42 ~ 53；
Ethylene glycol 0.5 ~ 2；
Crylic acid hydroxy ester 7 ~ 10；
Triethylamine 1 ~ 2.0；
Deionized water 9 ~ 13；
Catalyst is the 0.02 ~ 0.05% of above-mentioned raw materials gross mass；
Polymerization inhibitor is the 0.04 ~ 0.06% of above-mentioned raw materials gross mass；
Aqueous diluting monomer, for reconciling system viscosity for the 10 ~ 20% of above-mentioned raw materials gross mass.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that the cis-butenedioic anhydride purity grade is change
Learn pure.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that the trimethylolpropane it is pure
Degree rank is pure for chemistry.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described diisocyanate is adopted
It is following one or more：Toluene di-isocyanate(TDI)（TDI）, IPDI（IPDI）.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described polyether Glycols are using following
One or more：Polyethylene glycol -600（Molecular weight is 600）, PEG-8 00（Molecular weight is 800）.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that the purity grade of the ethylene glycol
It is pure to analyze.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described crylic acid hydroxy ester is adopted
With it is following one or more：Hydroxy-ethyl acrylate（HEA）, hydroxypropyl acrylate（HPA）.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described catalyst is adopted：February
Dilaurylate.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described polymerization inhibitor is using following
One or more：TBHQ, MEHQ.
Described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that described aqueous diluting monomer is
Water-soluble monomer, using it is following one or more：Tetrahydrofuran acrylate, N- acryloyl morpholines.
The preparation method of described cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that with following step
Suddenly：
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask suitable
Acid anhydride and trimethylolpropane, are to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determine acid number, when acid number reach it is predetermined
Value, adds appropriate aqueous diluting monomer, obtains performed polymer I.
（2）The synthesis of performed polymer II：Diisocyanate, catalyst are added to another four-hole boiling flask, and polyethers binary is added dropwise
Alcohol, is to slowly warm up to 85～90 DEG C after completion of dropping；Then, the h of insulation reaction 1, determines isocyanate group content, works as isocyanic acid
Ester group content reaches predetermined value, obtains base polyurethane prepolymer for use as II.
（3）The synthesis of performed polymer III：Under agitation, ethylene glycol and performed polymer I are added to performed polymer II, and is controlled anti-
Temperature is answered in 85～90 DEG C；Then, the h of insulation reaction 1, determine isocyanate group content, when isocyanate group content reach it is predetermined
Value, obtains performed polymer III.
（4）Under agitation, in 75～80 DEG C, in base polyurethane prepolymer for use as III crylic acid hydroxy ester is added.Then, exist
Under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base content is reduced to zero, is cooled to 45 DEG C and to reaction system
Interior addition triethylamine, question response system temperature is stable at 50 ~ 65 DEG C, adds appropriate amount of deionized water, and high-speed stirred（500 turns/
Minute）15 minutes, then obtain cis-butenedioic anhydride modified urethane acrylate water-base resin.
Beneficial effects of the present invention：
1st, the present invention introduces carboxyl by cis-butenedioic anhydride open loop, substitutes 2,2- dihydromethyl propionic acids or 2,2- dimethylolpropionic acid introduces parent
The effect of aqueous group, increased a kind of synthetic method of aqueous polyurethane acrylate.
2nd, cis-butenedioic anhydride modified urethane acrylate water-base resin prepared by the present invention, pliability is excellent, and paint film resistance to water is good
It is good.
Specific embodiment
Following number is parts by weight.
Embodiment 1：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.5；
Trimethylolpropane 2.0；
Toluene di-isocyanate(TDI) 26.4；
Polyether Glycols -600 45.4；
Ethylene glycol 1.4；
Hydroxy-ethyl acrylate 8.8；
Triethylamine 1.5；
Deionized water 12.9；
Catalyst dibutyltin dilaurylate is the 0.02% of gross mass；
Polymerization inhibitor TBHQ is the 0.04% of gross mass；
Aqueous diluting monomer tetrahydrofuran acrylate is the 10% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.5 parts of cis-butenedioic anhydrides and 2.0 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 10 parts of tetrahydrofuran acrylate are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：26.4 parts of toluene di-isocyanate(TDI)s, 0.02 part of two bay are added to another four-hole boiling flask
Sour dibutyl tin, and 45.4 parts of polyether Glycols -600 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then, it is incubated
1 h is reacted, isocyanate group content is determined, when isocyanate group content reaches predetermined value, base polyurethane prepolymer for use as II is obtained.
（3）The synthesis of performed polymer III：Under agitation, 1.4 parts of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, add in base polyurethane prepolymer for use as III 8.8 parts of hydroxy-ethyl acrylates and
0.04 part of polymerization inhibitor TBHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base
When content is reduced to zero, is cooled to 45 DEG C and 1.5 parts of triethylamines added into reaction system, question response system temperature it is stable 50 ~
When 65 DEG C, 12.9 parts of deionized waters, and high-speed stirred are added（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified polyurethane third
Olefin(e) acid ester water-base resin.
Embodiment 2：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.9；
Trimethylolpropane 2.6；
Toluene di-isocyanate(TDI) 22.8；
Polyether Glycols -800 52.3；
Ethylene glycol 0.8；
Hydroxy-ethyl acrylate 7.6；
Triethylamine 2.0；
Deionized water 9.8；
Catalyst dibutyltin dilaurylate is the 0.05% of gross mass；
Polymerization inhibitor MEHQ is the 0.05% of gross mass；
Aqueous diluting monomer N- acryloyl morpholines are the 15% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.9 parts of cis-butenedioic anhydrides and 2.6 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 15 parts of N- acryloyl morpholines are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：22.8 parts of toluene di-isocyanate(TDI)s, 0.05 part of two bay are added to another four-hole boiling flask
Sour dibutyl tin, and 52.3 parts of polyether Glycols -800 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then, it is incubated
1 h is reacted, isocyanate group content is determined, when isocyanate group content reaches predetermined value, base polyurethane prepolymer for use as II is obtained.
（3）The synthesis of performed polymer III：Under agitation, 0.8 part of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, add in base polyurethane prepolymer for use as III 7.6 parts of hydroxy-ethyl acrylates and
0.05 part of polymerization inhibitor MEHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base content drop
When being zero, it is cooled to 45 DEG C and 2.0 parts of triethylamines is added into reaction system, question response system temperature is stable at 50 ~ 65 DEG C, adds
9.8 parts of deionized waters, and high-speed stirred（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified urethane acrylate water-base resin.
Embodiment 3：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.8；
Trimethylolpropane 2.5；
Toluene di-isocyanate(TDI) 25.8；
Polyether Glycols -600 44.5；
Ethylene glycol 1.2；
Hydroxypropyl acrylate 9.6；
Triethylamine 1.9；
Deionized water 12.6；
Catalyst dibutyltin dilaurylate is the 0.02% of gross mass；
Polymerization inhibitor MEHQ is the 0.04% of gross mass；
Aqueous diluting monomer N- acryloyl morpholines are the 20% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.8 parts of cis-butenedioic anhydrides and 2.5 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 20 parts of N- acryloyl morpholines are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：25.8 parts of toluene di-isocyanate(TDI)s, 0.02 part of two bay are added to another four-hole boiling flask
Sour dibutyl tin, and 44.5 parts of polyether Glycols -600 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then, it is incubated
1 h is reacted, isocyanate group content is determined, when isocyanate group content reaches predetermined value, base polyurethane prepolymer for use as II is obtained.
（3）The synthesis of performed polymer III：Under agitation, 1.2 parts of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, add in base polyurethane prepolymer for use as III 9.6 parts of hydroxypropyl acrylates and
0.04 part of polymerization inhibitor MEHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base contains
When amount is reduced to zero, it is cooled to 45 DEG C and 1.9 parts of triethylamines is added into reaction system, question response system temperature is stable 50 ~ 65
DEG C when, add 12.6 parts of deionized waters, and high-speed stirred（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified polyurethane propylene
Acid esters water-base resin.
Embodiment 4：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.9；
Trimethylolpropane 2.6；
Toluene di-isocyanate(TDI) 22.6；
Polyether Glycols -800 51.9；
Ethylene glycol 0.8；
Hydroxypropyl acrylate 8.4；
Triethylamine 2.0；
Deionized water 9.7；
Catalyst dibutyltin dilaurylate is the 0.04% of gross mass；
Polymerization inhibitor TBHQ is the 0.06% of gross mass；
Aqueous diluting monomer tetrahydrofuran acrylate is the 20% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.9 parts of cis-butenedioic anhydrides and 2.6 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 20 parts of tetrahydrofuran acrylate are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：22.6 parts of toluene di-isocyanate(TDI)s, 0.04 part of two bay are added to another four-hole boiling flask
Sour dibutyl tin, and 51.9 parts of polyether Glycols -800 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then, it is incubated
1 h is reacted, isocyanate group content is determined, when isocyanate group content reaches predetermined value, base polyurethane prepolymer for use as II is obtained.
（3）The synthesis of performed polymer III：Under agitation, 0.8 part of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, 8.4 parts of hydroxypropyl acrylates and 0.06 are added in base polyurethane prepolymer for use as III
Part polymerization inhibitor TBHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base content is reduced to
When zero, it is cooled to 45 DEG C and 2.0 parts of triethylamines is added into reaction system, question response system temperature is stable at 50 ~ 65 DEG C, adds
9.7 parts of deionized waters, and high-speed stirred（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified urethane acrylate water-base resin.
Embodiment 5：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.4；
Trimethylolpropane 1.9；
IPDI 31.4；
Polyether Glycols -600 42.4；
Ethylene glycol 1.3；
Hydroxy-ethyl acrylate 8.2；
Triethylamine 1.4；
Deionized water 12.0；
Catalyst dibutyltin dilaurylate is the 0.02% of gross mass；
Polymerization inhibitor TBHQ is the 0.04% of gross mass；
Aqueous diluting monomer tetrahydrofuran acrylate is the 15% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.4 parts of cis-butenedioic anhydrides and 1.9 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 15 parts of tetrahydrofuran acrylate are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：To another four-hole boiling flask add 31.4 parts of IPDIs, 0.02 part two
Dibutyl tin laurate, and 42.4 parts of polyether Glycols -600 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then,
The h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches predetermined value, obtains base polyurethane prepolymer for use as II.
（3）The synthesis of performed polymer III：Under agitation, 1.3 parts of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, add in base polyurethane prepolymer for use as III 8.2 parts of hydroxy-ethyl acrylates and
0.04 part of polymerization inhibitor TBHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base
When content is reduced to zero, is cooled to 45 DEG C and 1.4 parts of triethylamines added into reaction system, question response system temperature it is stable 50 ~
When 65 DEG C, 12.0 parts of deionized waters, and high-speed stirred are added（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified polyurethane third
Olefin(e) acid ester water-base resin.
Embodiment 6：Cis-butenedioic anhydride modified urethane acrylate water-base resin of the present invention, has following weight to make than raw material：
Cis-butenedioic anhydride 1.8；
Trimethylolpropane 2.5；
IPDI 27.3；
Polyether Glycols -800 49.3；
Ethylene glycol 0.8；
Hydroxy-ethyl acrylate 7.1；
Triethylamine 1.9；
Deionized water 9.2；
Catalyst dibutyltin dilaurylate is the 0.04% of gross mass；
Polymerization inhibitor MEHQ is the 0.06% of gross mass；
Aqueous diluting monomer N- acryloyl morpholines are the 10% of gross mass.
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover.Add in four-hole boiling flask
Enter 1.8 parts of cis-butenedioic anhydrides and 2.5 parts of trimethylolpropanes, be to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determines acid number,
When acid number reaches predetermined value, 10 parts of N- acryloyl morpholines are added, obtain performed polymer I.
（2）The synthesis of performed polymer II：To another four-hole boiling flask add 27.3 parts of IPDIs, 0.04 part two
Dibutyl tin laurate, and 49.3 parts of polyether Glycols -800 are added dropwise, 85～90 DEG C are to slowly warm up to after completion of dropping；Then,
The h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches predetermined value, obtains base polyurethane prepolymer for use as II.
（3）The synthesis of performed polymer III：Under agitation, 0.8 part of ethylene glycol and performed polymer I are added to performed polymer II, and
Controlling reaction temperature is in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches
To predetermined value, performed polymer III is obtained.
（4）Under agitation, in 75～80 DEG C, add in base polyurethane prepolymer for use as III 7.1 parts of hydroxy-ethyl acrylates and
0.06 part of polymerization inhibitor MEHQ.Then, under the conditions of 85～90 DEG C, insulation reaction 1h, when system isocyanate base contains
When amount is reduced to zero, it is cooled to 45 DEG C and 1.9 parts of triethylamines is added into reaction system, question response system temperature is stable 50 ~ 65
DEG C when, add 9.2 parts of deionized waters, and high-speed stirred（500 revs/min）15 minutes, then obtain cis-butenedioic anhydride modified polyurethane propylene
Acid esters water-base resin.
Embodiment 7
With 80 parts of cis-butenedioic anhydride modified urethane acrylate water-base resin, 10 parts of N- acryloyl morpholines, 10 parts of deionized water, light-initiated
0.04 part of agent 2- hydroxy-2-methyl -1- phenyl -1- acetone is well mixed and is prepared into coating, is applied with 100 microns of thickness with bar
It is distributed in tinplate sheet, in irradiation intensity is 50 mW/cm after 80 DEG C of baking ovens baking 2min2Ultraviolet light under irradiation 20 seconds do
Dry film forming.Determine performance as follows：
Each performance test is carried out by GB, pliability test：GB/T 1731-93；
Adhesive force is tested：GB/T 9286-1998
Hardness test：GB/T6739-1996
Water resistance test：GB/T 1733-93.
Claims (8)
1. a kind of cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that be made up of following portions by weight：
Cis-butenedioic anhydride 1 ~ 2；
Trimethylolpropane 1 ~ 3；
Diisocyanate 22 ~ 32；
Polyether Glycols 42 ~ 53；
Ethylene glycol 0.5 ~ 2；
Crylic acid hydroxy ester 7 ~ 10；
Triethylamine 1 ~ 2.0；
Deionized water 9 ~ 13；
Catalyst is the 0.02 ~ 0.05% of above-mentioned raw materials gross mass；
Polymerization inhibitor is the 0.04 ~ 0.06% of above-mentioned raw materials gross mass；
Aqueous diluting monomer, for reconciling system viscosity for the 10 ~ 20% of above-mentioned raw materials gross mass；
The cis-butenedioic anhydride purity grade is pure for chemistry；
The purity grade of the trimethylolpropane is pure for chemistry.
2. the diisocyanate described in using it is following one or more：Toluene di-isocyanate(TDI)（TDI）, isophorone diisocyanate
Ester（IPDI）；
Cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that described polyethers two
First alcohol using it is following one or more：Polyethylene glycol -600（Molecular weight is 600）, PEG-8 00（Molecular weight is 800）.
3. cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that the ethylene glycol
Purity grade for analysis it is pure.
4. cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that described propylene
Sour hydroxy ester using it is following one or more：Hydroxy-ethyl acrylate（HEA）, hydroxypropyl acrylate（HPA）.
5. cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that described catalysis
Agent is adopted：Dibutyl tin laurate.
6. cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that described inhibition
Agent using it is following one or more：TBHQ, MEHQ.
7. cis-butenedioic anhydride modified urethane acrylate water-base resin according to claim 1, it is characterised in that described is aqueous
Diluting monomer is water-soluble monomer, using it is following one or more：Tetrahydrofuran acrylate, N- acryloyl morpholines.
8. a kind of preparation method of cis-butenedioic anhydride modified urethane acrylate water-base resin, it is characterised in that with following steps：
（1）The synthesis of performed polymer I：Four-hole boiling flask and mechanical agitator are installed on electric heating cover；Add in four-hole boiling flask suitable
Acid anhydride and trimethylolpropane, are to slowly warm up to 98～100 DEG C；Then, the h of insulation reaction 1, determine acid number, when acid number reach it is predetermined
Value, adds appropriate aqueous diluting monomer, obtains performed polymer I；
（2）The synthesis of performed polymer II：Diisocyanate, catalyst are added to another four-hole boiling flask, and polyether Glycols are added dropwise, dripped
Plus it is to slowly warm up to 85～90 DEG C after finishing；Then, the h of insulation reaction 1, determines isocyanate group content, works as NCO
Content reaches predetermined value, obtains base polyurethane prepolymer for use as II；
（3）The synthesis of performed polymer III：Under agitation, ethylene glycol and performed polymer I are added to performed polymer II, and controls reaction temperature
Spend in 85～90 DEG C；Then, the h of insulation reaction 1, determines isocyanate group content, when isocyanate group content reaches predetermined value,
Obtain performed polymer III；
（4）Under agitation, in 75～80 DEG C, in base polyurethane prepolymer for use as III crylic acid hydroxy ester is added；Then, 85～
Under the conditions of 90 DEG C, insulation reaction 1h, when system isocyanate base content is reduced to zero, is cooled to 45 DEG C and adds into reaction system
Enter triethylamine, question response system temperature is stable at 50 ~ 65 DEG C, add deionized water, and high-speed stirred（500 revs/min）15
Minute, then obtain cis-butenedioic anhydride modified urethane acrylate water-base resin.
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