CN101121770A - Water acrylic resin and preparing method thereof - Google Patents
Water acrylic resin and preparing method thereof Download PDFInfo
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- CN101121770A CN101121770A CNA2006100300124A CN200610030012A CN101121770A CN 101121770 A CN101121770 A CN 101121770A CN A2006100300124 A CNA2006100300124 A CN A2006100300124A CN 200610030012 A CN200610030012 A CN 200610030012A CN 101121770 A CN101121770 A CN 101121770A
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- Prior art keywords
- water
- acrylic resin
- initiator
- monomer
- mixture
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Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 51
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004945 emulsification Methods 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001412 amines Chemical group 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000002978 peroxides Chemical group 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000005502 peroxidation Methods 0.000 claims description 16
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 9
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 8
- 229960002887 deanol Drugs 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012972 dimethylethanolamine Substances 0.000 claims description 8
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical group COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- 239000012948 isocyanate Substances 0.000 abstract description 8
- 150000002513 isocyanates Chemical class 0.000 abstract description 8
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 239000006184 cosolvent Substances 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 2
- HZJLDCKPKZXWRA-UHFFFAOYSA-N butyl hydrogen carbonate;ethene Chemical group C=C.CCCCOC(O)=O HZJLDCKPKZXWRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000004816 latex Substances 0.000 abstract 1
- 229920000126 latex Polymers 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 239000003973 paint Substances 0.000 description 17
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 241000237502 Ostreidae Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The utility model relates to a water-based acrylic resin paintand the manufacturing method. The basic ray materials comprise acrylic monomer, styrene monomer, initiator, cosolvent, and active solvent. The utility model is characterized in that the acrylic monomer comprises acrylic derivative with hydroxyl; the cosolvent is ether alcohol solvent; the active solvent is butyl carbonate ethylene derivative active solvent; the initiator is peroxide initiator; and the neutralizer is Amine neutralizer. The resin is manufactured through two-step process. In the first step, water-based acrylic resin prepolymer is manufactured and is then manufactured into resin latex through inner emulsification on the second step. The product is of long storage time and is of no added emulsifier. Under the room temperature, the product can cross-link with water-based isocyanate curing agent to form membrane. The utility model is of excellent membrane, good water resistance, anti-scrubbing property, chemical resistance and sullying resistance.
Description
Technical field
The present invention relates to the coating industry in the chemical industry field, specifically, relate to a kind of basic raw material---the water-borne acrylic resin and preparation method thereof that uses in the water-borne coatings manufacturing.
Background technology
Along with the progress of society, the raising day by day of people's living standard, environmental protection more and more is subject to people's attention.All put into effect many relevant policy rules both at home and abroad, the discharging of hazardous and noxious substances has been given the restriction and the control of strictness.Coating industry is used the rich and influential family as organic solvent, has also more and more recognized this point and turns to and be devoted to develop water-borne coatings, thereby promoted the gradually increase of coating market to the water-borne coatings demand.Water-borne acrylic resin is because synthesize many advantages such as easy, that cost is low, organic volatile content (VOC) is low, be subjected to the favor of coating industry, coating with its preparation has good application property, gloss and paint film appearance, curing apparatus is simple, therefore, be widely used in fields such as building coating, fabric coating.
The method of traditional preparation process water-borne acrylic resin is that the Acrylic Acid Monomer mixture of employing band carboxyl is a raw material, prepares the polymkeric substance of being with carboxyl by polymerization, uses suitable alkali (as amine) neutralization then, to reach water-dispersion or water-soluble.Another kind of preparation method is by adding the emulsifying agent effect that tensio-active agent plays, impels polymkeric substance even dissolves in the water under the situation that does not have the water soluble group existence.The shortcoming of these two kinds of methods is owing to there is the residual or water miscible tensio-active agent of unreacted carboxylic group to assemble behind the coating curing, makes water tolerance, erosion resistance, resistance to bond, hardness and the levelling property etc. of paint film can not show a candle to the occasion of using the solvent-type acrylic cold coating.
Summary of the invention
The present invention not only is intended to solve the release problem of the ubiquitous poisonous and harmful solvent gas of common solvent type acrylic resin paint, but also overcome the deficiency of the water-borne acrylic resin of method for preparing, performances such as paint film property such as sticking power, solvent resistance, water tolerance are improved comprehensively, and hardness is adjustable, widely applicable.
The present invention realizes like this, described water-borne acrylic resin, use basic raw material comprise Acrylic Acid Monomer, styrene monomer, initiator, solubility promoter, strong solvent, it is characterized in that, comprised the acrylic acid derivative that contains hydroxyl in the used Acrylic Acid Monomer; Used solubility promoter is the ether alcohol kind solvent; Used strong solvent is a tertiary monocarboxylic acid derivatives active solvent; Used initiator is the peroxide initiator; Used neutralizing agent is the amine neutralizing agent, and the proportioning of each material component is as follows:
Acrylic Acid Monomer 10～50 quality %
Styrene monomer 10～30 quality %
Initiator 1～5 quality %
Solubility promoter 0～15 quality %
Strong solvent 10～50 quality %
Neutralizing agent 5～15 quality %.
Described here Acrylic Acid Monomer is meant the mixture of vinylformic acid and derivative thereof, comprise outside one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate and so on acrylic monomer commonly used, also comprise one or more the mixture that is selected from hydroxyethyl methylacrylate, Rocryl 410, the caprolactone.
Not only select the higher acrylic monomer of common polymerization activity for use as raw material monomer, but also comprised the acrylic acid derivative of hydroxyl, can make the acrylic resin that obtains have wetting ability preferably like this, improve the stability of the water-borne acrylic resin that makes.
Also comprise styrene monomer in the used raw material monomer of synthetic resin of the present invention, this is because styrene monomer can make cold coating have excellent dryness, hardness, gloss, fullness ratio, chemical proof and water tolerance after film forming.The styrene monomer that is suitable for comprise be selected between-a kind of in the vinyl toluene, p-methylstyrene, vinylbenzene or their mixture.Wherein the paint film property that is provided with methylic vinyl toluene monomer especially is more outstanding.
According to the present invention, the building-up reactions of resin causes by peroxide initiator, and the superoxide that is suitable for is selected from a kind of in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters or their mixture.Be suitable with peroxidation two tert-pentyl esters especially wherein, the structure of this superoxide is as follows:
A little less than being characterized in that free radical hydrogen-taking capacity that peroxidation two tert-pentyls self decompose to produce, cause crosslinked less in the polymerizable acrylic monomer process, therefore resin has molecular weight distribution preferably, viscosity is lower, the water-borne acrylic resin color and luster of making is better, hydroxyl in the resin is uniform distribution better also, and free monomer content is low, so the over-all properties of paint film is improved.
The solubility promoter that uses in this building-up reactions is preferably the ether alcohol kind solvent, can be selected from a kind of in propylene glycol butyl ether, the butyl glycol ether or their mixture.
The present invention's key character compared with prior art is: the present invention has introduced the tertiary monocarboxylic acid derivative as strong solvent in the polymerizable acrylic monomer process, contain the Hydroxylated acrylic resin prepolymer of hydrophilic radical and tertiary carbon base so as to preparation.Its structure is as follows:
In the formula: R
1, R
2, R
3Be alkyl substituent, have a methyl substituents at least, remaining substituting group is the straight or branched alkyl; The carbonatoms that is used for the tertiary monocarboxylic acid of coating generally is C9, C10, C11.R
4, R
5, R
6Be alkyl group.
This is a kind of two ester structures, contains nonpolar tertiary monocarboxylic acid group and oh group of a large volume.The effect of tertiary monocarboxylic acid group provides low viscosity and good pigment wettability, the compatibility with non-polar solvent, good anti-UV, excellent chemical resistant properties, height hydrophobic nature and crosslinked sterically hindered protective effect; And that oh group provides is crosslinked, interlayer adheres to and with the compatibility of polarity coating.Described tertiary monocarboxylic acid derivatives active solvent is selected from a kind of in tertiary carbonic acid glycidyl ester, the tertiary ethylene carbonate or their mixture.Be good with tertiary carbonic acid glycidyl ester especially wherein.Some excellent performances be can provide because in resin of the present invention, introduce tertiary carbonic acid glycidyl ester (for example, the Cardura E-10p that Shell Co. Ltd produces),, acid resistance and outdoor weather resisteant improved simultaneously as high solvent compatibility and low viscosity.Tertiary carbonic acid glycidyl ester is also referred to as the R-GLYCIDOL ester of tertiary monocarboxylic acid, and its structure is as follows:
In the formula: R
1, R
2, R
3Be alkyl substituent, have a methyl substituents at least, remaining substituting group is the straight or branched alkyl.The carbonatoms that is used for the tertiary monocarboxylic acid of coating generally is C9, C10, C11.
The constructional feature of tertiary carbonic acid glycidyl ester makes it become the properties-correcting agent of coating resin uniqueness, and its epoxy group(ing) has very strong reactive behavior, generally can react with hydroxyl, carboxyl and amido.In Acrylic Acid Monomer generation radical polymerization, tertiary carbonic acid glycidyl ester forms grafting by the carboxylic group reaction with Acrylic Acid Monomer.This graft reaction produces an oh group, and it can be used for the crosslinking reaction with solidifying agent.This reaction seldom or need not other solubilizing agent.This is because very low based on the acrylic resin of tertiary carbonic acid glycidyl ester viscosity under high solid and common synthesis temperature.The high boiling range of tertiary carbonic acid glycidyl ester (250～280 ℃) makes the temperature be reflected at 100～180 ℃ of scopes, preferably carries out under 150～155 ℃ of temperature and need not pressurization.Can produce low viscous product with this method with narrow molecular weight distributions.Owing to do not contain solvent, improved the ultimate production of effective product, thereby reduced the volume cost of solid resin.In addition, because of the existence of tertiary carbon base, surface tension is lower, and moisture content is contained in emulsion particle inside, and moisture content has certain plastification, can help film forming, and reaction equation is as follows:
The preparation of water-borne acrylic resin of the present invention divided for two steps: the first step is a preparation Hydroxylated acrylic resin prepolymer; Second step, with prepolymer emulsification, concrete steps comprised by internal emulsification technology:
(1) add solubility promoter and strong solvent in the reactor that stirring rake, thermometer and condenser are housed, logical nitrogen stirs and is warming up to 150～155 ℃;
(2) under this temperature, drip part propylene acid mono and derivative, styrene monomer and part initiator, dropping time 3.5～4.5h, insulation 0.3～1h, add remaining Acrylic Acid Monomer and part initiator, dropping time 0.3～1h, add remaining initiator at last rapidly, insulation 1.5～2.5h makes the acrylic resin prepolymer;
(3) above-mentioned prepolymer is cooled to 80～90 ℃, adds neutralizing agent, in the stirring and behind 25～35min, be cooled to 65～75 ℃, slowly drip deionized water emulsification, dropping time 1.5～2.5h fully stirs 25～35min discharging then.
So the water-based hydroxyl acrylic resin of the present invention preparation can well be dispersed into water-base resin in water mainly be by in the carboxyl on the molecular chain and salify and be subjected to the protection of tertiary carbon base simultaneously.Therefore the monomeric consumption of carboxyl group has directly influenced the water tolerance of resin, when this type of monomer is very few, mixed water-based hydroxyl acrylic resin has the visible small-particle and produces, the wetting ability that shows resin is not enough, when this type of monomeric consumption is excessive, though obtain the finely dispersed water-based hydroxyl acrylic resin of oyster white, but after use cured with isocyanates film forming, blushing is arranged, this is because very good wetting ability causes moisture to shed from paint film, therefore, carboxyl group monomer (for example acrylic or methacrylic acid) consumption is that 8～15% of synthesizing formula component total mass is advisable, after the prepared water-borne acrylic resin film forming, over-all properties the best.
Water-borne acrylic resin of the present invention be by in the amine and side chain on the carboxyl salify and be scattered in the water, the amine neutralizing agent that is suitable for is selected from one or more the mixture in dimethylethanolamine, trolamine, the ammoniacal liquor, wherein especially to use ammoniacal liquor comparatively cheap and convenient.Degree of neutralization is expressed by the pH value, and pH has directly influenced the performance of viscosity change, package stability and paint film.When the pH value was neutralized to 8.0～9.0, modest viscosity was uniformly dispersed, and the pH value reaches at 8.5 o'clock, particularly suitable (referring to table 1).
Table 1 pH value is to the influence of paint film transparency
| The pH value | Paint film appearance |
| 7.0 7.0～8.0 8.0～9.0 | Unglazed, surface have white mist more transparent, have that slightly white mist is transparent, gloss is better |
By as seen above-mentioned,, form the water-based hydroxyl acrylic resin according to being distributed in the water by internal emulsification in the Hydroxylated acrylic resin prepolymer of the present invention's preparation and behind the salify.Prepared ACRYLIC EMULSION particle diameter is very little, preparation technology's simple and stable, the product period of storage is long, do not contain the outer emulsifying agent that adds, at room temperature can with the crosslinked film forming of water-based isocyanate solidifying agent, have good film-forming properties, excellent in water resistance, scrub resistance, chemical proofing, anti-staining property, can be widely used in high-grade water-borne wood coating, watery anti-corrosion paint and water-based metal decorative paint etc.Water-borne acrylic resin of the present invention has typical performance as shown in table 2:
The typical performance of table 2 water-borne acrylic resin
| Test item | The development of this project |
| The outward appearance solid content, % viscosity, s pH value density, g/ml particle diameter, nm molecular weight distribution | Oyster white slightly transparent 35～40 60～150 8.0～9.0 1.02 200～600 2.4～3.0 |
Embodiment
With embodiment the present invention is described in further detail below, but the present invention never is confined to these embodiment.
Embodiment 1
The raw material of preparation water-borne acrylic resin is formed as shown in table 3.
Table 3 preparation water-borne acrylic resin (embodiment 1) is formed with raw material
| Component | Quality (g) |
| The propylene glycol butyl ether | 8.3 |
| Tertiary carbonic acid glycidyl ester | 24.7 |
| Vinylformic acid | 10.7 |
| Hydroxyethyl methylacrylate | 3.2 |
| Methyl methacrylate | 19.8 |
| Butyl acrylate | 7.5 |
| Vinylbenzene | 14.6 |
| Peroxidized t-butyl perbenzoate | 2.8 |
| Dimethylethanolamine | 8.4 |
| Deionized water | 160.0 |
Concrete preparation method is as follows: propylene glycol butyl ether and tertiary carbonic acid glycidyl ester are added in the 500mL four-hole boiling flask that thermometer, whipping appts and condenser are housed, feed the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Begin the mixture of dropwise addition of acrylic acid, hydroxyethyl methylacrylate, methyl methacrylate, butyl acrylate, vinylbenzene and peroxidized t-butyl perbenzoate then, vinylformic acid 7g wherein, peroxidized t-butyl perbenzoate 2.4g, in about 4 hours, add, temperature remains on 150～155 ℃, is incubated 0.5 hour; Add vinylformic acid 3.7g and peroxidized t-butyl perbenzoate 0.3g again, dripped in about 0.5 hour, add peroxidized t-butyl perbenzoate 0.1g immediately, temperature remains on 150～155 ℃, is incubated 2 hours, surveys solid content 90～92%; Material is cooled to 90～100 ℃, adds the dimethylethanolamine neutralization, fully stirred 15～20 minutes, survey pH value 8～9, be cooled to about 70 ℃, add deionized water and carry out emulsification, added in about 2 hours, fully stir discharging after 30～40 minutes.
Above-mentioned internal emulsification water-borne acrylic resin solids content is 37%, and the pH value is 8.5, and emulsion particle diameter is 500～600nm, and viscosity (coating with No. 4 cups) is 130s; Molecular weight distribution 2.7 is made aqueous woodware varnish lacquer with above-mentioned internal emulsification water-borne acrylic resin, and (for example Bai Haier 3100 of WT2102 of French Rhodia or German Bayer AG) is used with the water-based isocyanate solidifying agent, and performance is as shown in table 4:
The table 4 resinous coating property of embodiment 1 water-based acrylic acid
| Project | Detected result |
| 60 ° of gloss, % | 93 |
| Pencil hardness | H |
| The film forming situation | Good |
| Impact, kgcm | 50 |
| Snappiness, mm | 1 |
| Sticking power, level | 1 |
| Water tolerance, % (48h) | Slight loss of gloss |
| Wear resistance, (750g 300 changes) | 0.02g |
Annotate: 750g refers to counterweight weight on the elastic grinding wheel in the wear resistance, and 300 change the number of turns that refers to that elastic grinding wheel rotates.
As seen, aqueous woodware varnish lacquer and the supporting aspect excellent performances such as sticking power, gloss and shock-resistance that are applied in of water-based isocyanate solidifying agent made of the internal emulsification water-borne acrylic resin of present embodiment preparation.
Embodiment 2
The raw material for preparing water-borne acrylic resin is in this example formed as shown in table 5.As different from Example 1, improve the amount of methyl methacrylate in the material component in this example, reduced the amount of butyl acrylate, adopted vinyl toluene to replace vinylbenzene.
Table 5 preparation water-borne acrylic resin (embodiment 2) is formed with raw material
| Component | Quality (g) |
| The propylene glycol butyl ether | 8.3 |
| Tertiary carbonic acid glycidyl ester | 24.7 |
| Vinylformic acid | 10.7 |
| Hydroxyethyl methylacrylate | 3.2 |
| Methyl methacrylate | 21.0 |
| Butyl acrylate | 6.1 |
| Vinyl toluene | 14.8 |
| Peroxidized t-butyl perbenzoate | 2.8 |
| Dimethylethanolamine | 8.4 |
| Deionized water | 170.0 |
Concrete preparation method is as follows: propylene glycol butyl ether and tertiary carbonic acid glycidyl ester are joined in the 500mL four-hole boiling flask that thermometer, whipping appts and condenser are housed, feed the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Begin the mixture of dropwise addition of acrylic acid, hydroxyethyl methylacrylate, methyl methacrylate, butyl acrylate, vinyl toluene and peroxidized t-butyl perbenzoate then, vinylformic acid 7g wherein, peroxidized t-butyl perbenzoate 2.4g, in about 4 hours, add, temperature remains on 150～155 ℃, is incubated 0.5 hour; Add vinylformic acid 3.7g and peroxidized t-butyl perbenzoate 0.3g again, dripped in about 0.5 hour, add peroxidized t-butyl perbenzoate 0.1g immediately, temperature remains on 150～155 ℃, is incubated 2 hours, surveys solid content 90～92%; Material is cooled to 90～100 ℃, adds the dimethylethanolamine neutralization, fully stirred 15～20 minutes, survey pH value 8～9, be cooled to about 70 ℃, be added dropwise to deionized water and carry out emulsification, added in about 2 hours, fully stir discharging after 30～40 minutes.
Above-mentioned internal emulsification water-borne acrylic resin solids content is 36%, and the pH value is 8.5, and emulsion particle diameter is 500～600nm, and viscosity (coating with No. 4 cups) is 110s; Molecular weight distribution 3.0, this example is owing to improved the content of methyl methacrylate, and used vinyl toluene, therefore hardness and feel are better, water tolerance also is improved, the colored paint made from this water-base resin cooperates with water-based isocyanate solidifying agent WT2102 (French Rhodia produces), has good gloss, mechanical property and chemical proof, can be applicable to passenger car and decorates finish paint.Performance test results is as shown in table 6.
The table 6 resinous coating property of embodiment 2 water-based acrylic acids
| Test item | Detected result |
| Outward appearance | Surface free of pinholes and particle |
| Fineness | ＜15 |
| Solid content, % | 55 |
| Package stability, level | 8 |
| Two component coating working lives, h | 8 |
| Surface drying, h | 1 |
| Do solid work h | 8 |
| Bending property, mm | 1 |
| Sticking power, level | 1 |
| Drawing test, mm | 6 |
| Shock-resistance, Kcm | 50 |
| Pendulum-rocker hardness | 0.4 |
| 60 ° of gloss, % | 92 |
| Water tolerance (25 ± 1 ℃), h | 48h does not have foaming, wrinkling, and slight loss of gloss is arranged |
| Petrol-resistance 24h | Do not have foaming, wrinkling, slight loss of gloss and variable color are arranged |
| Chemical proofing, 3% sulfuric acid, 2%NaOH, 5%HAc | 15min appearance color no change |
| Opacifying power, g/m 2 | 105 |
| Non-volatile content content, % | 55 |
After present embodiment internal emulsification water-borne acrylic resin is made colored paint,, have the excellent comprehensive performance, gather around and have broad application prospects with the supporting application of water-based isocyanate solidifying agent.
Embodiment 3
Adopt peroxidation two tert-pentyls as initiator in this example, the raw materials used composition of preparation resin is as shown in table 7.
Table 7 preparation water-borne acrylic resin (embodiment 3) is formed with raw material
| Component | Quality (g) |
| The propylene glycol butyl ether | 8.2 |
| Tertiary carbonic acid glycidyl ester | 24.7 |
| Vinylformic acid | 10.7 |
| Hydroxyethyl methylacrylate | 3.2 |
| Methyl methacrylate | 19.8 |
| Butyl acrylate | 7.5 |
| Vinylbenzene | 14.6 |
| Peroxidation two tert-pentyls | 3.3 |
| Dimethylethanolamine | 8.0 |
| Deionized water | 160.0 |
Concrete preparation method is as follows: propylene glycol butyl ether and tertiary carbonic acid glycidyl ester are joined in the 500mL four-hole boiling flask that thermometer, whipping appts and condenser are housed, feed the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Begin the mixture of dropwise addition of acrylic acid, hydroxyethyl methylacrylate, methyl methacrylate, butyl acrylate, vinylbenzene and peroxidation two tert-pentyls then, vinylformic acid 7g wherein, peroxidation two tert-pentyl 2.9g added in about 4 hours, and temperature remains on 150～155 ℃ of insulations 0.5 hour; Add into vinylformic acid 3.7g and peroxidation two tert-pentyl 0.3g again, dripped in about 0.5 hour, add peroxidation two tert-pentyl 0.1g immediately, temperature remains on 150～155 ℃ of insulations 2 hours, surveys solid content 90～92%; Material is cooled to 90～100 ℃, adds the dimethylethanolamine neutralization, fully stirred 15～20 minutes, survey pH value 8～9, be cooled to about 70 ℃, be added dropwise to deionized water and carry out emulsification, added in about 2 hours, fully stir discharging after 30～40 minutes.
This routine internal emulsification water-borne acrylic resin solids content is 37%, and the pH value is 8.0, and emulsion particle diameter is 200～300nm, and viscosity (coating with No. 4 cups) is 60s; Molecular weight distribution 2.4, adopt peroxidation two tert-pentyls to make the internal emulsification water-based hydroxyl acrylic resin performance more excellent (performance is relatively shown in table 8 and 9) of initiator gained, but peroxidation two tert-pentyls cost an arm and a leg, the application of above routine resin be primarily aimed at high-grade fancy paint.
Table 8 uses the comparison of different initiator gained water-borne acrylic resin performances
| The initiator kind | Viscosity (being coated with 4 glasss) | Molecular weight distribution | Particle diameter (nm) | Package stability (45 ℃) |
| Peroxidation two tert-pentyls | 60s | 2.4 | 200-300 | 14 days no changes |
| Peroxidized t-butyl perbenzoate | 110s | 3.0 | 500-600 | A little layering was arranged in 14 days |
Table 9 uses water-based isocyanate solidifying agent WT2102 (French Rhodia) to solidify the comparison of the paint film property of back two kinds of varnish
| The initiator kind | Surface drying (h) | Gloss (60 °) | Pencil hardness | Sticking power |
| Peroxidation two tert-pentyls | 0.5 | 97 | H | 0 grade |
| Peroxidized t-butyl perbenzoate | 1.0 | 92 | F | 1 grade |
Claims (10)
1. water-borne acrylic resin, its basic raw material comprises Acrylic Acid Monomer, styrene monomer, initiator, solubility promoter, strong solvent, it is characterized in that, has comprised the acrylic acid derivative that contains hydroxyl in the used Acrylic Acid Monomer; Used solubility promoter is the ether alcohol kind solvent; Used strong solvent is a tertiary monocarboxylic acid derivatives active solvent; Used initiator is the peroxide initiator; Used neutralizing agent is the amine neutralizing agent, and the proportioning of each material component is as follows:
Acrylic Acid Monomer 10～50 quality %
Styrene monomer 10～30 quality %
Initiator 1～5 quality %
Solubility promoter 0～15 quality %
Strong solvent 10～50 quality %
Neutralizing agent 5～15 quality %.
2. water-borne acrylic resin according to claim 1, it is characterized in that, described Acrylic Acid Monomer is meant the mixture of vinylformic acid and derivative thereof, comprise outside one or more the mixture that is selected from vinylformic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate and so on acrylic monomer commonly used, also comprise one or more the mixture that is selected from hydroxyethyl methylacrylate, Rocryl 410, the caprolactone.
3. water-borne acrylic resin according to claim 1 is characterized in that, between described styrene monomer is selected from-and a kind of in the vinyl toluene, p-methylstyrene, vinylbenzene or their mixture.
4. water-borne acrylic resin according to claim 1 is characterized in that, described peroxide initiator is selected from a kind of in the peroxidation tert-butyl ester, peroxidation two tert-pentyl esters or their mixture.
5. water-borne acrylic resin according to claim 1 is characterized in that, described ether alcohol class solubility promoter is selected from a kind of in propylene glycol butyl ether, the butyl glycol ether or their mixture.
6. water-borne acrylic resin according to claim 1 is characterized in that, described tertiary monocarboxylic acid derivatives active solvent is selected from a kind of in tertiary carbonic acid glycidyl ester, the tertiary ethylene carbonate or their mixture.
7. water-borne acrylic resin according to claim 6 is characterized in that, described tertiary monocarboxylic acid derivatives active solvent is a tertiary carbonic acid glycidyl ester.
8. water-borne acrylic resin according to claim 1 is characterized in that, described amine neutralizing agent is selected from one or more the mixture in dimethylethanolamine, trolamine, the ammoniacal liquor.
9. the preparation method of the described water-borne acrylic resin of claim 1 is characterized in that, prepares this resin by the internal emulsification method, and concrete steps comprise:
(1) add solubility promoter and strong solvent in reactor, logical nitrogen stirs and is warming up to 150～155 ℃;
(2) under this temperature, drip part propylene acid mono and derivative, styrene monomer and part initiator, dropping time 3.5～4.5h, insulation 0.3～1h, add remaining Acrylic Acid Monomer and part initiator, dropping time 0.3～1h, add remaining initiator at last rapidly, insulation 1.5～2.5h makes the acrylic resin prepolymer;
(3) above-mentioned prepolymer is cooled to 80～90 ℃, adds neutralizing agent, in the stirring and behind 25～35min, be cooled to 65～75 ℃, slowly drip deionized water emulsification, dropping time 1.5～2.5h fully stirs 25～40min discharging then.
10. the preparation method of water-borne acrylic resin according to claim 9 is characterized in that, in the neutralization reaction operation, control pH value reaches 8.0～9.0.
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