CN1076376C - Modified acrylic resin and preparation method thereof - Google Patents
Modified acrylic resin and preparation method thereof Download PDFInfo
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- CN1076376C CN1076376C CN99112057A CN99112057A CN1076376C CN 1076376 C CN1076376 C CN 1076376C CN 99112057 A CN99112057 A CN 99112057A CN 99112057 A CN99112057 A CN 99112057A CN 1076376 C CN1076376 C CN 1076376C
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- acrylic resin
- initiator
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- monomer
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims abstract description 9
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 229920006163 vinyl copolymer Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- -1 (methyl) methyl Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
A modified acrylic resin for road paint is prepared from SBS styrene-butadiene rubber, vinyl copolymer monomer and chain transfer agent through free radical trigger polymerization in the presence of solvent, and features that the SBS styrene-butadiene rubber is free radical grafted to obtain thermoplastic acrylic resin with better antiwear nature. The adhesive force of the resin is 2 grade, the abrasion resistance is less than 45mg, the viscosity (second) is W-Y, and the solid content is more than 50 percent.
Description
The invention belongs to paint field, particularly relate to the thermoplastic acrylic resin of preparation coating or lacquer usefulness.
The acrylic resin in market is because of its look shallow now, rate of drying is fast, and moderate cost is applicable to the preparation road mark paint.Consumption in road mark paint is increasing in recent years.But because some defectives and deficiency that acrylic resin prescription and production technique exist are that the main coating that makes wears no resistance with it, the road mark paint of making is short work-ing life, has increased the cost of roadmarking virtually.
The object of the present invention is to provide a kind of the acrylic resin modified of road paint that be used to make.It has the thermoplastic acrylic resin of better wear resistance because resin has been carried out modified rubber, can be used for preparing road mark paint.
Another object of the present invention is to provide the preparation method of this acrylic resin.
The present invention realizes by the following technical solutions: the characteristics of this resin are prepared the thermoplastic acrylic resin with grafting rubbers for SBS styrene-butadiene rubber(SBR) is carried out free yl graft polymerization.Be that this acrylic resin is with SBS styrene-butadiene rubber(SBR), copolyethylene monomer, has or do not have the mixture of chain-transfer agent, in the presence of solvent, make by the radical initiator polymerization.It is characterized in that in the copolyethylene monomer of synthesizing propylene acid resin, adding SBS styrene-butadiene rubber(SBR).
The copolyethylene monomer of resin of the present invention comprises (methyl) alkyl acrylate, unsaturated carboxylic acid, and other vinyl monomers.
The proportioning of each monomer component is in this resin:
SBS styrene-butadiene rubber(SBR) 0.2-5%
(methyl) alkyl acrylate 45-98%
Unsaturated carboxylic acid 0.5-4%
Other vinyl monomers 0-50%.
The used SBS styrene-butadiene rubber(SBR) consumption of the present invention is the 0.2-5% that accounts for the monomer total amount, is lower than at 0.2% o'clock, and the resin of preparation can not show the raising of wear resistance, is higher than at 5% o'clock, and resin is difficult to control when synthetic, gelling easily takes place.
Wherein used (methyl) alkyl acrylate is meant (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA etc.
Adoptable unsaturated carboxylic acid is meant vinylformic acid, methacrylic acid, methylene-succinic acid etc.
Spendable other vinyl monomers comprise vinylbenzene, alpha-methyl styrene, vinyl cyanide, (methyl) acrylamide, N hydroxymethyl acrylamide, N, N-dimethyl matrix acrylamide etc.Other vinyl monomers are for adding in resin of the present invention, and it is mainly in order to reduce the raw materials cost of this resin.
Comprise that as the example of the initiator of the generation free radical of acrylic resin of the present invention benzoyl peroxide, dicumyl peroxide, tertbutyl peroxide, azo two isobutyls are fine etc.Initiator common consumption be 1-5% (accounting for the copolyethylene monomer meter), preferably 2-3%.
Can generate radical initiator can a collection ofly add, and also the different steps in reaction process adds in batches.The initiator of resin of the present invention adds usually in three batches, and first is the 30-70% of the total add-on of initiator, and second batch is 20-40%, and the 3rd batch is 10-30%.
Also can use chain-transfer agent when preparing this resin, as lauryl mercaptan, butanethiol, mercaptoethanol, thiohydracrylic acid etc.Chain-transfer agent be available can.The consumption of chain-transfer agent is the 0-40% of initiator amount.
Method of the present invention is to carry out in the presence of solvent, prepare the used solvent of this resin hydro carbons, ester class and ketones solvent are arranged, particularly varsol such as toluene, benzene, esters solvent such as N-BUTYL ACETATE, vinyl acetic monomer, ketones solvent such as methyl iso-butyl ketone (MIBK), methylethylketone, acetone.
The polymeric reaction temperature of resin of the present invention is relevant with the boiling point of solvent, promptly carries out under the boiling point of solvent.At 1: 4 o'clock, its reflux temperature was 82-87 ℃ as the ratio of toluene and benzene.
Acrylic resin modified preparation method of the present invention is as follows:
In the reactor that thermometer, stirrer, reflux exchanger, water trap, dropping funnel and nitrogen conduit are housed, add solvent and SBS rubber, the limit imports the nitrogen limit and is warming up to backflow (as the ratio of toluene and benzene at 1: 4 o'clock, its reflux temperature is 82-87 ℃), return time is 20 minutes to 1 hour, with the mixture of copolyethylene monomer ((methyl) alkyl acrylate, unsaturated carboxylic acid, other vinyl monomers), radical initiator and chain-transfer agent, by in 4 hours, slowly adding with dropping funnel with uniform velocity.Drip off back insulation 1 hour, it is an amount of to add radical initiator then, and drip half an hour.Be incubated after 0.5-1.5 hour, add a certain amount of radical initiator again, with dripping off half an hour.Insulation 1-3 hour under reflux temperature afterwards, it is even to add an amount of stirring solvent again, cooling, filters and promptly gets this resin.
Can help further to understand the present invention with following embodiment.
Embodiment 1
In the reactor that thermometer, stirrer, reflux exchanger, water trap, dropping funnel and nitrogen conduit are housed, add 56 parts of toluene, 219 parts of benzene, 5 parts of SBS rubber, the limit imports the nitrogen limit and is warming up to 85 ℃ of reflux temperatures, reflux half an hour, with 260 parts of methyl methacrylates, 180 parts of butyl acrylates, 10 parts in vinylformic acid, 50 parts of vinylbenzene, the mixture that benzoyl peroxide is 5 parts added with dropping funnel with uniform velocity in 4 hours.Drip off back insulation 1 hour, add 3.6 parts of benzoyl peroxides then, drip half an hour.Be incubated after 1 hour, add 2.6 parts of benzoyl peroxides, half an hour again and drip off.Be incubated 2 hours afterwards under refluxing, add 112.5 parts of toluene, 112.5 parts of benzene again, cooling is filtered and is promptly got this resin.
Its key technical indexes is as follows:
1, sticking power is 2 grades
2, wear resistance (mg/1000g, 200 change) 43.3
3, viscosity (second) W-Y
4, solid part 52%
And not adding the acrylic resin of SBS rubber under the equal conditions, its wear resistance is 53.8mg.
Embodiment 2
In the reactor identical with embodiment 1, add toluene 80 grams, vinyl acetic monomer 220 grams, SBS rubber 10 grams, importing nitrogen limit, limit is warming up to 80 ℃, and the mixture that methyl methacrylate 230 restrains, butyl acrylate 90 restrains, 2-EHA 50 restrains, vinylformic acid 10 restrains, vinylbenzene 120 restrains, benzoyl peroxide 6 restrains and lauryl mercaptan 0.6 restrains was added with uniform acceleration in 4 hours.Drip off back insulation 1 hour, add benzoyl peroxide 3 grams then, partly for a short time having added.Be incubated after 2 hours, add benzoyl peroxide 2 gram, half an hour again and drip off.Be incubated 2 hours afterwards under refluxing, add toluene 200 grams again, cooling is filtered and is promptly got this resin.To be 2 grades, viscosity (pressing Jia Nashi-Hall moral bubble viscosity representation) be W-Y second, solid part 50% to its sticking power, and its wear resistance rises to 40.4mg by the 54.1mg that does not add SBS rubber.
System lacquer example:
With 40 parts of this resins, 12 parts of titanium dioxides, 10 parts of talcum powder, 7 parts of light calcium carbonates, 9 parts of silica powders, 0.5 part of organobentonite, 2 parts of dibutyl phthalates, 16 parts of toluene, 2 parts of N-BUTYL ACETATEs, 1.5 parts in butanols, 1.5 parts of mixed lacquers of methyl alcohol, be ground to below the fineness 60 μ m, obtain the index of road mark paint: solid content 62%, viscosity 100 seconds, wear resistance 42mg.Other index all meets the JL/T280-1995 requirement.
Claims (8)
1, a kind ofly is used for the acrylic resin modified of road paint, it is characterized in that in the copolyethylene monomer of synthesizing propylene acid resin, adding SBS styrene-butadiene rubber(SBR), SBS styrene-butadiene rubber(SBR) is carried out free radical grafting, and the consumption of SBS styrene-butadiene rubber(SBR) accounts for 0.2-5% of monomer total amount.
2, acrylic resin according to claim 1 is characterized in that said copolyethylene monomer comprises (methyl) alkyl acrylate, unsaturated carboxylic acid, and other vinyl monomers.
3, acrylic resin according to claim 1 and 2 is characterized in that the consumption of said copolymerization of ethylene monomer component is:
(methyl) alkyl acrylate 45-98%
Unsaturated carboxylic acid 0.5-4%
Other vinyl monomers 0-50%.
4, a kind of preparation method of acrylic resin according to claim 1, it is characterized in that in reactor, add solvent and the SBS rubber that accounts for monomer total amount 0.2-5%, the limit imports the nitrogen limit and is warming up to backflow, return time is 20 minutes to 1 hour, with the mixture of copolyethylene monomer, radical initiator and chain-transfer agent, in 4 hours, slowly add with dropping funnel with uniform velocity; Drip off back insulation 1 hour, add an amount of initiator then, drip half an hour, is incubated after 0.5-1.5 hours, adds a certain amount of radical initiator again, with dripping off half an hour, is incubated 1-3 hours afterwards under reflux temperature, adds an amount of solvent again.
5, the preparation method of acrylic resin according to claim 4 is characterized in that the common consumption of said initiator is 1-5% (accounting for the copolyethylene monomer meter).
6, the preparation method of acrylic resin according to claim 5 is characterized in that said preferred initiator amount is 2-3%.
7, according to the preparation method of claim 4 or 5 or 6 described acrylic resins, it is characterized in that initiator is to add in three batches, first is that to be the 20-40%, three batch be 10-30% for 30-70%, the second batch of the total add-on of initiator.
8, according to the preparation method of claim 4 or 5 or 6 described acrylic resins, the consumption that it is characterized in that said chain-transfer agent is 0-40% of an initiator amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112057A CN1076376C (en) | 1999-01-29 | 1999-01-29 | Modified acrylic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112057A CN1076376C (en) | 1999-01-29 | 1999-01-29 | Modified acrylic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1228457A CN1228457A (en) | 1999-09-15 |
| CN1076376C true CN1076376C (en) | 2001-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112057A Expired - Fee Related CN1076376C (en) | 1999-01-29 | 1999-01-29 | Modified acrylic resin and preparation method thereof |
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| Country | Link |
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| CN (1) | CN1076376C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775101B (en) * | 2010-02-05 | 2011-11-02 | 广东工业大学 | Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof |
| CN106046994A (en) * | 2016-08-09 | 2016-10-26 | 王建周 | Flame retardant non-benzene solvent marking paint |
| CN115197589B (en) * | 2021-04-08 | 2023-09-22 | 长沙族兴新材料股份有限公司 | Polymer coated aluminum pigment with high metal effect and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105447A (en) * | 1985-07-11 | 1987-01-14 | 成都科技大学 | Make the short-cut method of graft copolymers |
| CN1060662A (en) * | 1990-10-05 | 1992-04-29 | 黑蒙特股份公司 | The mixture of the graft copolymer of amphoteric polymeric material and the graft copolymer of olefinic rubber material |
| CN1065664A (en) * | 1991-03-29 | 1992-10-28 | 三菱丽阳株式会社 | The preparation method who contains the graft copolymer particles of rubber |
| CN1133316A (en) * | 1996-01-29 | 1996-10-16 | 郑振乾 | Light reflection sign for road and adhesion agent preparation method |
-
1999
- 1999-01-29 CN CN99112057A patent/CN1076376C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105447A (en) * | 1985-07-11 | 1987-01-14 | 成都科技大学 | Make the short-cut method of graft copolymers |
| CN1060662A (en) * | 1990-10-05 | 1992-04-29 | 黑蒙特股份公司 | The mixture of the graft copolymer of amphoteric polymeric material and the graft copolymer of olefinic rubber material |
| CN1065664A (en) * | 1991-03-29 | 1992-10-28 | 三菱丽阳株式会社 | The preparation method who contains the graft copolymer particles of rubber |
| CN1133316A (en) * | 1996-01-29 | 1996-10-16 | 郑振乾 | Light reflection sign for road and adhesion agent preparation method |
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| Publication number | Publication date |
|---|---|
| CN1228457A (en) | 1999-09-15 |
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