CN101497680B - Alcohol water-soluble copolymer resin, preparation and application thereof - Google Patents
Alcohol water-soluble copolymer resin, preparation and application thereof Download PDFInfo
- Publication number
- CN101497680B CN101497680B CN2009100056294A CN200910005629A CN101497680B CN 101497680 B CN101497680 B CN 101497680B CN 2009100056294 A CN2009100056294 A CN 2009100056294A CN 200910005629 A CN200910005629 A CN 200910005629A CN 101497680 B CN101497680 B CN 101497680B
- Authority
- CN
- China
- Prior art keywords
- component
- acid
- acrylate
- epoxy
- resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920006026 co-polymeric resin Polymers 0.000 title abstract description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 22
- 229920003023 plastic Polymers 0.000 claims description 22
- 239000004033 plastic Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229960004756 ethanol Drugs 0.000 description 13
- 238000007599 discharging Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides alcohol-water soluble multivariated copolymer resin consisting of vinyl acetate, epoxide resin, unsaturated acid, acrylic ester and monomer of a hydrophile functional group, and having a structure that the epoxide resin is taken as a fork chain. The invention has the advantages that the copolymer resin not only has excellent cementability, flexibility and curing capability and low cost, but also can be dissolved in alcohol or component solvent of alcohol and water, reduce the dosage of organic solvent and prevent the environment pollution. The invention also provides the preparation method of the copolymer resin and the application of the copolymer resin used as complex gum and dope after being cured by amine at room temperature.
Description
Technical field
The present invention relates to a kind of alcohol water-soluble copolymer resin, particularly by vinyl acetate between to for plastic, Resins, epoxy, unsaturated acid, acrylate and hydrophilic functional groups monomer synthetic alcohol water-soluble copolymer resin, its preparation method with as the application of composite gum, coating.Belong to chemical field.
Background technology
Resins, epoxy is the thermoset macromolecule material that a class has performances such as good bonding, erosion resistance, high strength, has been widely used in multiple metal and nonmetallic bonding.It is big that bisphenol A type epoxy resin solidifies the back cross-linking density, and highly cross-linked structure has been brought the shortcoming of poor toughness, has limited its application in some technical field.Existing epoxy resin and acrylic ester copolymer is varied, with the modified epoxy acrylate resin that Resins, epoxy and acrylate are made, has improved the toughness of film forming matter.The epoxy resin and acrylic ester copolymer generally can only adopt organic solvents such as benzene class or ketone to make thinner as composite gum and coating the time, and the use cost height is big for environment pollution, has limited its application.
Summary of the invention
The object of the present invention is to provide a kind of alcohol water-soluble copolymer and its production and use.This multipolymer is formed by the multiple monomer copolymerization of vinyl acetate between to for plastic, Resins, epoxy, unsaturated acid, acrylate and hydrophilic functional groups, its snappiness strengthens, easily drying and forming-film and have environmental protection, technology is simple and advantages of cheap price.
Alcohol water-soluble copolymer provided by the invention is prepared from by the polymerizable monomer solution of following weight proportion:
Vinyl acetate between to for plastic 20～44%
Resins, epoxy 10～25%
Unsaturated acid 2～5%
Acrylate 43～55%
Hydrophilic functional groups monomer 1～5%
Add the initiator Diisopropyl azodicarboxylate or the benzoyl peroxide of above-mentioned monomer total amount 0.1～1.0%, form as solvent polymeric with ethanol or Virahol.
Described Resins, epoxy is bisphenol A epoxide resin; Unsaturated acid is acrylic acid or the like and polyunsaturated polycarboxylic acid; Acrylate is alkyl ester, vinylformic acid and the glycidyl methacrylate of vinylformic acid and 1～8 carbon atom of methacrylic acid; The hydrophilic functional groups monomer is binary unsaturated acid, vinylformic acid and derivative thereof.
Wherein bisphenol A epoxide resin is E
44Or E
51Unsaturated acid is vinylformic acid, methacrylic acid, maleic acid or FUMARIC ACID TECH GRADE; Acrylate is at least a or several mixture in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, Isooctyl acrylate monomer, (methyl) glycidyl acrylate; Hydrophilic functional groups monomer vinylformic acid and derivative thereof are at least a or several mixture in vinylformic acid, methacrylic acid and acid amides thereof, hydroxyl acid amides, the hydroxyalkyl.
Alcohol water-soluble copolymer involved in the present invention can be used the amine curing agent self-vulcanizing, is mixed with composite gum; It also can be mixed with coating with urea-formaldehyde resin, resol, Synolac or terpolycyantoamino-formaldehyde resin.Amine curing agent is the mixture of fat polyamine and 30～40% formalins, and the preferred fat polyamines is quadrol, hexanediamine, diethylenetriamine.
Alcohol water-soluble copolymer resin provided by the invention, concrete preparation method is:
A) bisphenol A epoxide resin E
44Or E
51With unsaturated acid by weight 10～25: 2～5, make solvent with alcohol, at 50 ℃～100 ℃, react the unsaturated acid-Resins, epoxy affixture that can obtain content 50%～90% in 1～8 hour.
B) the water-soluble multiple copolymer of synthol of preparing burden in the following order
First component vinyl acetate between to for plastic 10～22%
Add ethanol or Virahol, add-on is 0.5～1.5 times of above-mentioned vinyl acetate between to for plastic weight
Second component vinyl acetate between to for plastic 10～22%
Unsaturated acid-Resins, epoxy affixture 12～30%
Acrylate 43～55%
Hydrophilic functional groups monomer 1～5%
Initiator 0.1～1.0%
Add ethanol or Virahol, add-on is 0.3～1 times of above-mentioned second component total amount
C) the first component is added in the polymeric kettle, stir and be warming up to 70 ℃～75 ℃ of reflux temperatures.
D) slowly the second component is splashed in the still under stirring, reflux temperature, the time of dropping always is 4～6 hours.
E) drip off the back 70 ℃～80 ℃ reactions 1～2 hour.
F) according to the product concentration requirement, add ethanol or alcohol/water solvent dilution, cool to below 50 ℃, get final product discharging.The solid content of gained copolymer solution is 50%～75%.
Multiple copolymer provided by the invention is a kind of alcohol-water-soluble new system.The characteristics of alcohol water-soluble copolymer of the present invention are: (1) cost is low: main raw material of the present invention is a vinyl acetate between to for plastic, and these raw material sources are abundant and cheap; (2) feature of environmental protection: existing modified epoxy acrylate resin uses aromatic hydrocarbons, ester class or alkoxide to make solvent, and multipolymer of the present invention can be dissolved in the mixed solvent of alcohol or alcohol and water, has reduced the consumption of organic solvent, has avoided environmental pollution; (3) solidification value: the epoxy modified acrylic resin that is used to prepare composite gum, coating at present generally adopts hot setting mode (solidification value is up to 130～150 ℃), and resin of the present invention can adopt the amine curing agent self-vulcanizing; (4) snappiness strengthens: contain a large amount of soft monomer chain links in the macromolecular chain of the present invention, second-order transition temperature is lower, and the snappiness of multipolymer significantly improves.
Alcohol water-soluble copolymer of the present invention is used for fields such as composite gum, coating, has the production technique advanced person: facility investment is few, easy to operate, energy consumption is low, the characteristics and the advantage of the discharging of no noxious pollutant.It is applied as composite gum or coating has been given new function, a kind of efficient, environmental protection, new selection easily are provided.
The present invention will be further described below by embodiment, but be not limitation of the present invention.According to foregoing of the present invention, according to the ordinary skill knowledge and the customary means of this area,, can also make modification, replacement or the change of other various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite, all belong to the scope of protection of the invention.
Embodiment
Embodiment 1: the preparation example of alcohol water-soluble copolymer
In the reactor that whipping appts, reflux exchanger, heating temperature control and Dropping feeder are housed, add the mixing solutions of forming by following component successively.Earlier the first component is added in the reactor, stirring, heat temperature raising are to 70 ℃～75 ℃ of reflux temperatures; The second component is slowly added in the reactor, and the time of dropping always is 6 hours, dropwises the back and continues 75 ℃～80 ℃ reactions 1 hour; The third component thinner is slowly added in the still cooling discharging.Make the alcohol water-soluble copolymer solution 151kg of solid content 66%.
First component: vinyl acetate between to for plastic 15kg
Ethanol or Virahol 15kg
Second component: vinyl acetate between to for plastic 10kg
90% vinylformic acid-epoxy adduct 20kg
Butyl acrylate 50kg
Hydroxyethyl acrylate 3kg
Vinylformic acid 2kg
Diisopropyl azodicarboxylate 1kg
Third component: ethanol 31kg
Deionized water 4kg
Embodiment 2: the preparation example of alcohol water-soluble copolymer
In the reactor that whipping appts, reflux exchanger, heating temperature control and Dropping feeder are housed, add the mixing solutions of forming by following component successively.Earlier the first component is added in the reactor, stirring, heat temperature raising slowly add the second component in the reactor then to 75 ℃～80 ℃ of reflux temperatures, and the time of dropping always is 4 hours, dropwise the back and continue 75 ℃～80 ℃ reactions 2 hours; The third component thinner is slowly added in the still cooling discharging.Make the alcohol water-soluble copolymer solution 165.7kg of solid content 60%.
First component: vinyl acetate between to for plastic 21kg
Ethanol or Virahol 25kg
Second component: vinyl acetate between to for plastic 20kg
FUMARIC ACID TECH GRADE-epoxy adduct (90%) 12kg
Butyl acrylate 30kg
Methyl methacrylate 14kg
Hydroxyethyl acrylate 2kg
Methacrylic acid 1kg
Benzoyl peroxide 0.7kg
Third component: ethanol 30kg
Deionized water 10kg
Embodiment 3: alcohol water-soluble copolymer prepares the example of composite gum
In the reactor that whipping appts, reflux exchanger, heating temperature control and Dropping feeder are housed, add the mixing solutions of forming by following component successively.Earlier the first component is added in the reactor, stirring, heat temperature raising slowly add the second component in the reactor then to 70 ℃～75 ℃ of reflux temperatures, and the time of dropping always is 5 hours, dropwise the back and continue 75 ℃～80 ℃ reactions 2 hours; The third component thinner is slowly added in the still cooling discharging.Make the alcohol water-soluble copolymer solution 145.8kg of solid content 69%.
First component: vinyl acetate between to for plastic 20kg
Ethanol or Virahol 15kg
Second component: vinyl acetate between to for plastic 18kg
90% methacrylic acid-epoxy adduct 15kg
Methyl acrylate 20kg
Butyl acrylate 24kg
Propylene glycol monoacrylate 2kg
Vinylformic acid 1kg
Diisopropyl azodicarboxylate 0.8kg
Third component: ethanol 26kg
Deionized water 4kg
Alcohol water-soluble copolymer ambient temperature curable preparation dry-type composite glue by embodiment 3 preparations.
The preparation of solidifying agent:
In the reactor that whipping appts, reflux exchanger, heating temperature control and Dropping feeder are housed, add the mixing solutions of forming by following component successively.The first component is added stir in the still earlier and be warming up to 40 ℃; In 2 hours, slowly the second component is added in the still and 40 ℃ of reactions 1 hour; Add 95% industrial alcohol 14kg, cooling discharging.Make the solidifying agent 55kg of content 20%.
First component: formaldehyde (30～40%) aqueous solution 2.5kg
95% industrial alcohol 15kg
Second component: quadrol 10kg
95% industrial alcohol 15kg
The dry type compound tense, press following set of dispense system two-pack composite gum:
Component one alcohol water-soluble copolymer (69%) 90kg
Component two solidifying agent (20%) 5kg
Ethanol 100～200kg of moisture 10～20%
Embodiment 4: alcohol water-soluble copolymer prepares the example of coating
In the reactor that whipping appts, reflux exchanger, heating temperature control and Dropping feeder are housed, add the mixing solutions of forming by following component successively.Earlier the first component is added in the reactor, stirring, heat temperature raising are to 70 ℃～75 ℃ of reflux temperatures; The second component is slowly added in the reactor, and the time of dropping always is 5.5 hours, dropwises the back and continues 75 ℃～80 ℃ reactions 1 hour; The third component thinner is slowly added in the still cooling discharging.Make the alcohol water-soluble copolymer solution 150.6kg of solid content 65%.
First component: vinyl acetate between to for plastic 15kg
Ethanol or Virahol 20kg
Second component: vinyl acetate between to for plastic 20kg
90% maleic acid-epoxy adduct 15kg
Butyl acrylate 25kg
Methyl methacrylate 20kg
Hydroxyethyl methylacrylate 3kg
Vinylformic acid 2kg
Benzoyl peroxide 0.6kg
Third component: ethanol 28kg
Deionized water 4kg
Alcohol water-soluble copolymer by embodiment 4 preparations can be used for preparing alcohol-soluble and water-soluble coating.Its preparation technology is as follows:
Component one: alcohol water-soluble copolymer solution 50kg
Urea-formaldehyde resin (non-volatile part 60%) 2.5kg
Dehydrated alcohol 25kg
Deionized water 22.5kg
Component two: quadrol 6kg
Dehydrated alcohol 2.5kg
Deionized water 1.5kg
Two components are mixed formulated two-pack alcohol-soluble and water-soluble coating products 110kg.
Claims (7)
1. alcohol water-soluble copolymer, it has the structure that Resins, epoxy is side chain, and the oxirane value that it is characterized in that this multipolymer is 0.026～0.065, and it is by following weight proportion monomer component:
Vinyl acetate between to for plastic 20～44%
Resins, epoxy 10～25%
Unsaturated acid 2～5%
Acrylate 43～55%
Hydrophilic functional groups monomer 1～5%
Make by solution polymerization in the mixed solvent of alcohol, water, the solid content of copolymer solution is 50%～75%;
Described unsaturated acid is vinylformic acid, methacrylic acid, maleic acid or FUMARIC ACID TECH GRADE; Described hydrophilic functional groups monomer is vinylformic acid, methacrylic acid and acid amides thereof, hydroxyl acid amides, hydroxyalkyl at least a or several mixture wherein;
The preparation method comprises following steps:
1) Resins, epoxy and unsaturated acid by weight 10～25: 2～5, make solvent with alcohol, heat 50～100 ℃, react 1～8 hour, make unsaturated acid-Resins, epoxy affixture;
2) in the following order and weight batching
First component: vinyl acetate between to for plastic 10～22%
The alcoholic solvent that adds 0.5～1.5 times of weight of vinyl acetate between to for plastic
The second component:
Vinyl acetate between to for plastic 10～22%
Unsaturated acid-Resins, epoxy affixture 12～30%
Acrylate 43～55%
Hydrophilic functional groups monomer 1～5%
The initiator that adds monomer total amount 0.1～1.0%
3) the first component is added in the polymeric kettle, stir and be warming up to 70～75 ℃ of reflux temperatures;
4) slowly the second component is splashed in the still under stirring, reflux temperature, the dropping time is 4～6 hours;
5) drip off the back 70～80 ℃ of reactions 1～2 hour;
6) add the dilution of ethanol or Virahol, water solvent, cool to 50 ℃ with bottom discharge, copolymer solution.
2. alcohol water-soluble copolymer according to claim 1, wherein Resins, epoxy is bisphenol A epoxide resin; Acrylate is alkyl ester, vinylformic acid and the glycidyl methacrylate of vinylformic acid and 1～8 carbon atom of methacrylic acid.
3. alcohol water-soluble copolymer according to claim 2, wherein bisphenol A epoxide resin is E
44Or E
51Acrylate is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, Isooctyl acrylate monomer, (methyl) glycidyl acrylate at least a or several mixture wherein.
4. the preparation method of the described alcohol water-soluble copolymer of claim 1 is characterized in that it is synthetic by following steps:
1) Resins, epoxy and unsaturated acid by weight 10～25: 2～5, make solvent with alcohol, heat 50 ℃～100 ℃, react 1～8 hour, make unsaturated acid-Resins, epoxy affixture;
2) in the following order and weight batching
First component: vinyl acetate between to for plastic 10～22%
The alcoholic solvent that adds 0.5～1.5 times of weight of vinyl acetate between to for plastic
The second component:
Vinyl acetate between to for plastic 10～22%
Unsaturated acid-Resins, epoxy affixture 12～30%
Acrylate 43～55%
Hydrophilic functional groups monomer 1～5%
The initiator that adds monomer total amount 0.1～1.0%
3) the first component is added in the polymeric kettle, stir and be warming up to 70 ℃～75 ℃ of reflux temperatures;
4) slowly the second component is splashed in the still under stirring, reflux temperature, the dropping time is 4～6 hours;
5) 70 ℃～80 ℃ were reacted 1～2 hour;
6) add ethanol or Virahol, water solvent dilution, cool to below 50 ℃.
5. preparation method according to claim 4 is characterized in that: step 2) described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
6. the application of the arbitrary described alcohol water-soluble copolymer of claim 1～3 in preparation composite gum or coating.
7. coating is characterized in that: formulated by the arbitrary described alcohol water-soluble copolymer of claim 1～3 and urea-formaldehyde resin, resol, Synolac, terpolycyantoamino-formaldehyde resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100056294A CN101497680B (en) | 2008-02-02 | 2009-01-20 | Alcohol water-soluble copolymer resin, preparation and application thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810045343.4 | 2008-02-02 | ||
| CN200810045343 | 2008-02-02 | ||
| CN2009100056294A CN101497680B (en) | 2008-02-02 | 2009-01-20 | Alcohol water-soluble copolymer resin, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497680A CN101497680A (en) | 2009-08-05 |
| CN101497680B true CN101497680B (en) | 2011-02-09 |
Family
ID=40944964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100056294A Expired - Fee Related CN101497680B (en) | 2008-02-02 | 2009-01-20 | Alcohol water-soluble copolymer resin, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497680B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
| BR112012022175A2 (en) | 2010-03-04 | 2016-10-25 | Avery Dennison Corp | non pvc film and non pvc laminate |
| CN102382506B (en) * | 2011-08-02 | 2013-11-06 | 周贤永 | Water-soluble environmentally-friendly gravure ink and preparation method thereof |
| MY168809A (en) | 2012-02-20 | 2018-12-04 | Avery Dennison Corp | Multiplayer film for multi-purpose inkjet systems |
| US20150183544A1 (en) | 2013-12-30 | 2015-07-02 | Avery Dennison Corporation | Label Application System |
| CN106589313B (en) * | 2015-10-14 | 2020-09-04 | 中国石油化工股份有限公司 | Unsaturated acid modified epoxy resin universal carbon fiber sizing agent, preparation method and application thereof |
| CN106366825A (en) * | 2016-10-09 | 2017-02-01 | 常州亚环环保科技有限公司 | Preparation method of water-based anticorrosive paint |
-
2009
- 2009-01-20 CN CN2009100056294A patent/CN101497680B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497680A (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497680B (en) | Alcohol water-soluble copolymer resin, preparation and application thereof | |
| CN101921357B (en) | High-solid low-viscosity hydroxy acrylic resin and preparation process thereof | |
| CN101993670B (en) | Preparation method of active group containing polyacrylate flexibilizer | |
| US6599455B2 (en) | Process for producing wood particleboard | |
| EP1932860B1 (en) | An alcohol soluble resin and a method for preparing the same | |
| CN101747594A (en) | Epoxy acrylate prepolymer resin and preparation method thereof and application in photocurable coating | |
| CN101704932B (en) | Method for preparing coating resin from waste polystyrene plastics | |
| CN103387637B (en) | A kind of water-soluble self-crosslinking acrylic resin composition and method of making the same | |
| CN103613698A (en) | Thermosetting acrylic resin for powder coating as well as synthesis method and applications of thermosetting acrylic resin | |
| CN102925094A (en) | Ultraviolet light polymerization adhesive and preparation method thereof | |
| CN101747491A (en) | Fast thickening vinyl ester resin as well as preparation method and application thereof | |
| CN101962430B (en) | Production method of ultraviolet light curing amino acrylate resin | |
| CN103059209A (en) | Weather-resistant resin for hot-stamping film and preparation method of resin | |
| CN111961191B (en) | Epoxy curing agent for joint king and preparation method thereof | |
| CN101195232A (en) | Rice-wheat haulm plywood and process technique thereof | |
| CN101497770B (en) | Alcohol water-soluble modified epoxy composite glue and preparation thereof | |
| CN101974280A (en) | Pure epoxy type powder coating and preparation method thereof | |
| CN102060964B (en) | Preparation method and application of amino acrylic resin | |
| EP0597948B1 (en) | Polyacrylates and their use as levelling agents for powder coatings | |
| CN102363640A (en) | Acrylic ester powdered resin having self-cleaning property and synthesizing method thereof | |
| CN106752723A (en) | A kind of water-base epoxy antiseptic varnish and preparation method thereof | |
| CN102352212B (en) | High-strength metal adhesive and preparation method thereof | |
| CN106700986A (en) | Preparation method and product of high-strength double-component acrylic ester adhesive | |
| CN106832093A (en) | A kind of water-soluble thermoplastic acrylic resin and preparation method thereof | |
| CN103694836A (en) | UV (ultraviolet) photo-curable finish coat and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20090805 Assignee: Changshu Guohe New Materials Co., Ltd. Assignor: Zhong Wenjun Contract record no.: 2013510000013 Denomination of invention: Alcohol water-soluble copolymer resin, preparation and application thereof Granted publication date: 20110209 License type: Common License Record date: 20130407 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Changshu Guohe New Materials Co., Ltd. Assignor: Zhong Wenjun Contract record no.: 2013510000013 Date of cancellation: 20130730 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110209 Termination date: 20180120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |