CN101787231B - Hydrophobic modified association type thickening agent and preparation method thereof - Google Patents
Hydrophobic modified association type thickening agent and preparation method thereof Download PDFInfo
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- CN101787231B CN101787231B CN201010101863XA CN201010101863A CN101787231B CN 101787231 B CN101787231 B CN 101787231B CN 201010101863X A CN201010101863X A CN 201010101863XA CN 201010101863 A CN201010101863 A CN 201010101863A CN 101787231 B CN101787231 B CN 101787231B
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 37
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000008719 thickening Effects 0.000 claims abstract description 105
- 239000000178 monomer Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 83
- 239000000839 emulsion Substances 0.000 claims description 81
- 239000003995 emulsifying agent Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- -1 allyl ethers Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 7
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 239000012874 anionic emulsifier Substances 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- KBTAJPTUZHUSNQ-UHFFFAOYSA-N methoxymethane;methyl prop-2-enoate Chemical compound COC.COC(=O)C=C KBTAJPTUZHUSNQ-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 239000003973 paint Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 150000003254 radicals Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 238000009413 insulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001680 brushing effect Effects 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical group [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 230000003872 anastomosis Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a hydrophobic modified associative thickener and a preparation method thereof, wherein a hydrophobic modified monomer (such as SEM-25), an unsaturated carboxylic acid monomer and a carboxylic acid group-free mono-olefinic unsaturated monomer are adopted to prepare the associative thickener by a free radical emulsion polymerization method, the viscosity of an aqueous coating can be effectively improved by the obtained associative thickener, the shear resistance of the aqueous coating can be improved, and the thickener can obtain a better thickening effect under the condition of lower usage amount. The thickening agent can be added into the water-based paint to meet different requirements on viscosity of the water-based paint in different using processes.
Description
Technical field
The present invention relates to hydrophobic modified associative thickener, specifically the present invention relates to carry out the hydrophobic modified associative thickener of viscosity adjustment and enhancing shear resistant aqueous dispersion.
Background technology
The enhancing of Along with people's environmental consciousness and environmental regulation are to the restriction of organic volatile solvent, and it is the traditional coating and the paint of disperse phase that aqueous dispersion or water-based paint just replace with the organic solvent in growing field.Simultaneously, have advantages such as organic solvent-free, no disaster hidden-trouble, easy construction, easy cleaning because of it, be widely used in the building trade in modern times.Water-based paint is storing and there is different requirement in the stage such as construction to the viscosity of system: in storage process, be cohesion and the deposition that prevents pigment, need system to have certain viscosity; In the brushing process, require the viscosity of system to reduce along with the increase of shearing force, make it to have brushing property preferably; After brushing finished, the recovery of system viscosity preferably had of short duration retardation time, makes the levelling of filming; Require coating that certain viscosity is arranged before in case fluid stopping is hung in brushing with dry.This all need use thickening material.Suitable use thickening material can make rubber-emulsion paint obtain good fluid characteristics simultaneously; High-shear of balance coating and low shear flow performance; Both can avoid the deposited phenomenon in the storage process; The levelling in the time of can solving coating application again and the contradictory problems of sagging are given coating good preservation stability and application property.
The water-based paint thickening material can be divided into non-association type or claim common thickening material and associative thickener according to its thickening mechanism.Between the common thickening material molecule or itself and do not had direct association between the thickening polymer molecule; Its thickening power is to form macromolecular solution through the alkali-soluble polymer dissolving; Sometimes also make its alkali dissolve the back and form in external phase that certain reticulated structure realizes through slight chemically crosslinked; This type thickening material generally is a water-soluble polymer, under high shear rate the effect not obvious, like Natvosol and ROHM emulsion.Associative thickener is one type of hydrophobically modified water-soluble polymers, they can associate through hydrophobic association effect or ion-dipole interaction and emulsion particle (referring to Ma, Colloids Surf.A1996 such as Z.Y., 112,163; Quadrat, J.Prog.Org.Coat.2001 such as O., 42,110; And Reuvers, A.J.Prog.Org.Coat.1999,35,171.); Form reticulated structure, play thickening power, like hydrophobically modified caustic solubility ROHM emulsion, hydrophobically modified urethane, Natrosol Plus.
People such as nineteen eighty-three Emmons have delivered the patent of making the water-based paint thickening material with acrylic amide and chain alkyl N-substituted acrylamide multipolymer.After this patents of a lot of relevant associative thickeners have been emerged, like USP No. 4514552, No. 5292828 etc.These caustic solubility thickening materials normally contain the water miscible liquid reaction product of following material: (A) monoene key unsaturated carboxylic acid; Like methylacrylic acid; (B) be different from the monoethylenically unsaturated monomer of monomer (A), as ethyl propenoate with (C) contain hydrophobic part and can with monomer (A) and monomer (B) polymeric function monomer.
About the more existing reports of the preparation method of hydrophobic thickener emulsion, method is more than a kind of, as emulsion polymerisation process (referring to Jassal, M. etc.; J.Appl.Polym.Sci.2003,89,1430), the inverse emulsion polymerization method (referring to Pabon .J.Appl.Polym.Sci.2002 such as M.; 84,1418), precipitation polymerization process (referring to Zhuang, Polymer such as D.Q. 2002,43; 2075) and mini-emulsion polymerization method (referring to Pierce, EP such as C.G. 1309635,2005) etc.Letex polymerization utilizes water to be dispersion medium, can avoid utilizing that organic dispersion medium brings such as problems such as cost is high, shelf stability is poor, solvent removal, environmental pollution and health, has the unexistent characteristics of other method.So the present invention also adopts emulsion polymerisation process.
Summary of the invention
The present invention aims to provide a kind of hydrophobic modified associative thickener that improves water-miscible paint or water-based paint system viscosity and anti-shear performance and preparation method thereof; Compare with traditional thickening material; This kind thickening material can be issued to same viscosity or higher viscosity in the situation that add-on obviously reduces; The particularly important is thickening material of the present invention and have better anti-shear ability, can in wideer interval, regulate, therefore have more universality by the fluid property of thickened systems than traditional thickening material.
Thickening material of the present invention is the polymkeric substance that is obtained through the free-radical emulsion polymerization reaction by following material: one, unsaturated carboxylic acid monomer; Two, carboxy-containing acid group's monoethylenically unsaturated monomer not; Three, contain in the molecule hydrophobic part and can with (A) and (B) macromonomer of component generation radical polymerization, the i.e. unsaturated amphipathic function monomer of olefinic.
Technical scheme of the present invention is following:
A kind of hydrophobic modified associative thickener is made through the free-radical emulsion polymerization method by following three kinds of monomers:
A. unsaturated carboxylic acid monomer is selected from methylene-succinic acid, butene dioic acid, acrylic or methacrylic acid;
B. carboxy-containing acid group's monoethylenically unsaturated monomer not is selected from vinylbenzene, vinyl acetic monomer, methyl acrylate, ethyl propenoate, propyl acrylate or methacrylic ester;
C. the unsaturated amphipathic function monomer of olefinic, be selected from polyethoxye (20) methylacrylic acid stearyl, polyethoxye (25) methylacrylic acid mountain Yu base ester, stearyl polyethoxye (10) allyl ethers, gather (methyl) vinylformic acid (terepthaloyl moietie) ester, gather (terepthaloyl moietie) monomethyl ether (methyl) propenoate, ROHM (terepthaloyl moietie) ester with gather (terepthaloyl moietie) monomethyl ether mono acrylic ester or triphenyl ethyl phenoxy polyethoxye (25) ether metacrylic acid ester.The number of multiple ethoxy unit in the numeral wetting ability oxyethyl group segment in the bracket, this is the routine sign of this area.
More than three types of monomeric mass parts following: C.15～45 part B.130～190 part A.80～120 part,,, the solid content of gained thickening material is 28～32wt%.
Above-mentioned monomer A is vinylformic acid and methylacrylic acid preferably, most preferable vinylformic acid.
The preferred ethyl propenoate of above-mentioned monomers B.
Above-mentioned monomer C preferred triphenyl ethyl phenoxy polyethoxye (25) ether metacrylic acid ester is called for short SEM-25, is the triphen ethylphenol T 46155 methacrylic ester that contains 25 oxygen ethene chain links and polynary phenyl ring.Structural formula is as shown in the formula I:
The preparation method of the above-mentioned hydrophobic modified associative property thickening material of the present invention adopts emulsion polymerization, comprises the steps:
(1) 200～280 parts of water and 1.5～2 parts of emulsifying agents are added in the preparatory emulsor; Stir adding monomer A monomers B and the mixed solution of monomer C and the linking agent that accounts for these three kinds of monomer total mass 0.05%-0.5% down, after stirring 30-40min under the 600-800 rev/min of stir speed (S.S.), obtaining pre-emulsion.
The consumption of monomer A, B, C. is as previously mentioned: A.80～120 part, and B.130～190 part, C.15～45 part.
(2) 1/20 of the pre-emulsion that makes in 300～350 parts in water, 1.5～2 parts of emulsifying agents and the step (1) is added in the reactor drum; Under 150～200 rev/mins of stir speed (S.S.)s, stir; Be warming up to 75-90 ℃, add the aqueous solution that contains 0.025～0.035 part of initiator, wherein water is 0.5～1.0 part.Begin to react timing.
When (3) reaction is carried out 20-25 minute; Step (1) pre-emulsion with residual content is added drop-wise in the reactor drum with 0.35～0.45 part of initiator constant speed in 3 hours that is dissolved in 80～100 parts of water again; Add 0.05～0.10 part of initiator in 5～15 parts of water that is dissolved in for preparing after adding again; Be incubated 1-2 hour, promptly get thickening material.
Letex polymerization need use emulsifying agent to obtain stable product; The used emulsifying agent of the present invention is the combination of anionic emulsifier and nonionic emulsifier mass ratio 0.5～2.0; Wherein, Preferred X 2073 of anionic emulsifier or sodium sulfate, one of the preferred OP-9 of nonionic emulsifier or OP-21 or combination.
Preferred anionic type emulsifying agent and nonionic emulsifier are pressed 1: 1 combination of mass ratio.The total consumption of emulsifying agent (being the summation of emulsifying agent consumption in above-mentioned steps 1 and 2) accounts for the 0.1-5% of monomer total mass, preferably accounts for the 1.0-3.0% of monomer total mass.Can obtain the narrower polymer emulsion of stable size distribution under these conditions.
For the emulsion thickener that makes preparation has thickening preferably and anti-shear performance, preferred, the consumption of monomer C (promptly like SEM-25) is the 5.0-25wt% of monomer total mass in the above-mentioned steps (1), preferably accounts for the 8.0-20.0wt% of monomer total mass.
Used initiator initiator system of ammonium persulfate, Potassium Persulphate or Sodium Persulfate in the method for the present invention, the initiator dosage accounts for the 0.05-0.5% of monomer total mass, preferred 0.1%-0.3%.Thereby action of evocating is to produce the polymerization that radical causes vinyl monomer through thermolysis in the emulsion thickener, and what the present invention used is the water soluble starter persulphate.Most preferably initiator is an ammonium persulphate.
Temperature is very big to the influence of polyreaction.Speed of reaction was slow when temperature of reaction was low; The too high meeting of temperature of reaction reduces stability of emulsion even causes breakdown of emulsion.The preferred 75-90 of the present invention ℃ can make speed of reaction balanced, obtains the polymeric articles of ideal performance.
In order to improve thickening effectiveness, when in above-mentioned steps (1), preparing pre-emulsion, add the linking agent that accounts for monomer total mass 0.05%-0.5% synchronously with monomer.Said linking agent is selected from Viscoat 295, Vinylstyrene, ethylene glycol diacrylate, glycol methacrylate or Phthalic acid, diallyl ester.The linking agent dosage preferably accounts for the 0.1-0.3% of monomer total mass, and most preferably the linking agent dosage is 0.2% of a monomer total mass.
The preferred Phthalic acid, diallyl ester of above-mentioned linking agent (being called for short DAP), dosage is the 0.1-0.3% of monomer total mass.
The a spot of linking agent of adding has material impact to the performance of thickening material in the process of preparation.Do not add linking agent, the linear polymer that polymerization makes is dissolving fully under high pH, can not form tridimensional network, and thickening effectiveness is bad.Degree of crosslinking is too high, and the alkali that can restrict polymkeric substance dissolves, and also is difficult to reach the thickening effectiveness of expection, more existing reports this was carried out research (referring to Jassal M, wait J.Appl.Polym.Sci., 2003,89:1430; Prog.Org.Coat. such as Quadrat O, 2003,46:1).Degree of crosslinking (being the mass ratio that cross-linked polymer accounts for whole polymkeric substance) should be controlled at below 30% generally speaking.The monomer of realizing crosslinked polymer must possess two perhaps compounds of above unsaturated ethylene linkage, and Viscoat 295, Vinylstyrene, ethylene glycol diacrylate, glycol methacrylate and Phthalic acid, diallyl ester etc. all can be used as linking agent and be used for the present invention.
The effect experiment and the application of hydrophobically modified associative thickener of the present invention
Thickening material of the present invention to be can add in the water-borne coatings, satisfies in the different uses of water-borne coatings the demands of different to viscosity.
For making thickening material that excellent thickening effect take place, hydrophobically modified associative thickener of the present invention in use answers the pH of regulation system to alkalescence, and preferred pH scope is to be 7.4-9.0, and preferred pH scope is 8.1-8.7.Only under alkaline condition, under the promptly high pH value condition, alkali can take place and dissolve in the thickening material polymer molecule.Thickening material in use heightening pH makes in the emulsion dissolving of copolymer latices grain become the effect that macromolecular solution can reach thickening to alkalescence.Emulsion particle generation alkali is dissolved can use mineral alkali, mineral alkali is selected from sodium hydroxide, Pottasium Hydroxide or volatile caustic.
The present invention has prepared the hydrophobically modified thickening material through carboxy-containing acid group's in monoene key unsaturated carboxylic acid and the monomers B in unsaturated thiazolinyl on the hydrophobically modified monomer C and the monomer A monoethylenically unsaturated monomer copolymerization.According to the present invention, compare with common thickening material, the thickening material emulsion that contains the preparation of this modified monomer except possessing stronger anti-shear performance, through regulating its add-on, also can be to effectively being regulated in very wide scope by the viscosity of thickened systems.
Be to be the effect experiment of example with hydrophobically modified monomer SEM-25 below:
The viscosity of using Ubbelohde viscometer to measure the associative thickener of the different SEM-25 content that (capillary viscometer diameter 1.0-1.1mm) make the present invention is tested with the variation of pH.The main ingredient that plays thickening effect in view of this invention is monomer C, for ease of statement, the prepared thickening material of the present invention is numbered with the amount of its contained monomer C (SEM-25).T00 be the embodiment of the invention 6 controlled trials preparations do not contain the monomeric sample of C; T50 is the sample that contains 5.0% monomer C of the embodiment of the invention 3 preparations; T11 is the sample that contains 1.1% monomer C of the embodiment of the invention 5 preparations, and T120 is the sample that contains 12.0% monomer C of the embodiment of the invention 1 preparation.Table 1 the 2nd row have provided the content of corresponding monomer C.Table 1 has been enumerated the accessible peak viscosity of different thickening material emulsions (corresponding pH is between 7.5 to 8.1).It is all lower that this table 1 is illustrated under the low-solid content various thickening material viscosity, and under 0.5% concentration or lower situation, the viscosity of associative thickener solution is still not as traditional not hydrophobically modified thickening material.But when improving thickening material solid content to 0.65%, SEM-25 is that the viscosity of 12% associative thickener solution is apparently higher than not hydrophobically modified thickening material T00.Table 2 has provided the Brookfield ultimate viscosity number that should the series associative thickener changes with its solid content, and table 2 shows that solid content reaches at 1.0% o'clock, and the T50 that contains SEM-255.0% also is superior to the thickening material of non-modified.More than two list datas show that no matter be to use which kind of characterizing method, the hydrophobically modified thickening material reaches and all shows excellent thickening effect behind the finite concentration.
The peak viscosity that the thickening material emulsion reaches during the different solid content of table 1
In the table
*Monomer C content means that function monomer C accounts for the mass percent of A, B two monomer summations.
The viscosity of associative thickener emulsion when different solid content of the different SEM-25 content of table 2
In the table
*.Brookfield DV-II+Pro type rotational viscosimeter, No. 4 rotors, 20 rev/mins, room temperature measuring.
Judgement to the thickening material performance should not depended on the viscosity or the rheological property of itself merely, and answers emphasis to consider its Practical Performance in the water-based paint system.Get solid content and be 25% technical benzene acrylic emulsion; To the thickening material that wherein adds different SEM-25 content respectively, make it account for 1.0～2.5% of polymer solids quality in the benzene emulsion, transfer pH to 7.4 with 1mol/L NaOH solution; Adopt Brookfield DV-II+Pro type rotational viscosimeter; Use No. 4 rotors under the room temperature, the viscosity of mensuration system under 20 rev/mins of rotating speeds, the result lists in table 3.
Viscosity after the thickening of table 3 benzene emulsion is with the variation of thickening material addition
*. amount of thickener accounts for the mass percent of polymkeric substance in the benzene emulsion.
It is pointed out that the 1st row thickening material add-on in the table 3 is that amount with styrene-acrylic polymer in the system is that benchmark calculates, in view of being 25% by thickening benzene emulsion solid content, for whole emulsion, the concentration of thickening material is then much lower.The 2nd row have provided the relative concentration of thickening material in whole emulsion that adds in the table 3.Obviously; The hydrophobically modified thickening material that the present invention relates to; As long as its SEM-25 content reaches 5.0% (T50) in the thickening material polymkeric substance; Add-on reaches by 1.5% (perhaps in whole emulsion, reaching 0.37%) of thickening phenylpropyl alcohol multipolymer, the thickening thickening effectiveness of system just obviously is superior to the not hydrophobically modified product of correspondence.
Compare with the common thickening material of hydrophobically modified not, the associative thickener that carries out modification with SEM-25 has shear-stable performance preferably, a little less than promptly the viscosity of system reduces relatively when shearing rate raises.The thickening material that with the solid content is 1.0wt% experimentizes, and the pH to 8.3 of regulation system adopts Brookfield DV-II+Pro type rotational viscosimeter, changes stir speed (S.S.), and following No. 4 rotors of room temperature are measured its viscosity, and data are listed in table 4.Data show viscometer rotor speed are increased to 100 rev/mins by 0.5 rev/min; Unmodified traditional thickening material T00 viscosity is reduced to 1/35 of initial value; And the corresponding viscosity reduction of hydrophobically modified thickening material T11 of the present invention, T50 and T120 is respectively 1/26,1/33 and 1/31 of initial value, and promptly the hydrophobically modified thickening material diminishes with the viscosity reduction that shearing force increases correspondence.
The viscosity of thickening material emulsion under different shear rate of table 4 1.0wt% solid content
Contain hydrophobic grouping among the elite monomer C of the present invention; Wherein hydrophilic long-chain can stretch its molecular chain at water after alkali dissolved; And the hydrophobic grouping on it can be assembled in the conditional diffusion of water and because of it has the hydrophobic effect, produce bunch shape agglomerate or the body that associates thus, thereby make macromolecular chain produce intramolecularly and intermolecular association; Therefore change by the rheological of thickened systems, main effect is obviously to increase its viscosity.Obviously, the formation of this bunch of shape agglomerate or the body that associates needs finite concentration, and the minimum concentration that can produce this associative structure is called the critical association concentration of thickening material.Thickening material is only at it more than critical association concentration, and just possibly form with intermolecular association is master's supramolecular structure, thereby embodies thickening property preferably.The thickening properties of thickening material is to be determined by the character of the hydrophobic group that is connected and molecular structure to a great extent, therefore selects suitable hydrophobically modified monomer particularly important.The hydrophobically modified monomer of selecting among the present invention is triphen ethylphenol polyethenoxy ether metacrylic acid ester (the SEM-25 structural formula as follows); Contain polyoxyethylene chain and polynary phenyl ring in the molecule; Wherein the T 46155 chain length is 25 monomeric units; Can assist of the stretching, extension of thickening material molecule, increase the range of scatter of different thickening material molecule hydrophobic groupings, come in contact the probability that forms the association body between them thereby improve at water.
Excellent results of the present invention is following:
Among the present invention acrylic thickeners is carried out hydrophobically modified, obtain the hydrophobically modified caustic solubility ROHM emulsion of excellent property.This type thickening material in use needs the pH of regulation system.Under alkaline condition; Carboxylic acid becomes carboxylate salt in the multipolymer; Negative charge repels each other makes molecular chain become extended configuration from rolled state, and the molecular chain of thickening material polymkeric substance is dissolved in aqueous phase fully, and ionized carboxyl and water form the hydrated ion attitude; Reduce the flowability of water molecules; The more important thing is the hydrophobic modified thickening material that the present invention designs owing to be connected with a hydrophobic group through one than long wetting ability oxyethyl group on its molecule, long wetting ability oxyethyl group can launch at water, and the hydrophobic group between the differing mol can reconfigure and form a lyophobic association body.Owing to possibly contain a plurality of hydrophobic groupings on a thickening material copolymer molecule; Hydrophobic grouping on the same polymer chain can add different above-mentioned lyophobic association bodies; Thereby having formed with this hydrophobic association body is the three-dimensional netted polymkeric substance secondary structure of anastomose point, causes emulsion viscosity to increase.The amount of content through regulating hydrophobic grouping in the thickening material polymkeric substance or the thickening material that in by thickening emulsion, adds, the fluid property that can obtain to expect.Compare with the coventional type thickening material,, make the anti-shear ability of this type of thickening material improve greatly owing to can form the three-dimensional netted polymkeric substance secondary structure that this hydrophobic association body is an anastomose point in the hydrophobically modified thickening material.
Embodiment
Below in conjunction with embodiment the present invention is described further, but is not limited thereto.
The abbreviation of the related component among the embodiment is following:
MAA: methylacrylic acid (monomer A), EA: ethyl propenoate (monomers B), SEM-25: triphenyl ethyl phenoxy polyethoxye (25) ether metacrylic acid ester (monomer C).
DAP: Phthalic acid, diallyl ester (linking agent).
SDBS: X 2073, OP-9: oxygen ethene chain length is 9 polyoxyethylene nonylphenol, OP-21: oxygen ethene chain length is 21 polyoxyethylene nonylphenol.
Embodiment 1: the preparation of hydrophobically modified associative thickener
The composition of emulsifying agent: X 2073: OP-9: OP-21 mass ratio 2: 1: 1.
In preparatory emulsor, add 222.1g water, 2.0g emulsifying agent; Stir and add 109.7g MAA (methylacrylic acid down; Monomer A); 164.8g EA (ethyl propenoate, monomers B) and 0.55g linking agent Phthalic acid, diallyl ester (DAP) mixed solution and 33.0g SEM-25 (monomer C) obtain the 532.2g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 26.6g) of getting 360.0g water, 1.9g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in 0.028g initiator ammonium persulfate (APS) aqueous solution in the 1.0g water in advance.
The reaction beginning was added drop-wise to remaining 505.6g pre-emulsion and the 0.03g initiator A PS solution constant speed in 3 hours that is dissolved in 95.5g water in the reactor drum in back 20 minutes again.Temperature of reaction remains on 85 ℃.After adding, pre-emulsion adds the 0.1g initiator A PS that is dissolved in advance in the 12.0g water again, insulation 1h.Make that SEM-25 accounts for A, B two monomer total amounts are the thickening material (T120 in table 1～4) of 12.0wt%, its pH is 3.6, and the emulsion particle diameter is 120nm., adopt Brookfield DV-II+Pro type rotational viscosimeter (following No. 3 rotors of room temperature, 60 rev/mins), recording emulsion viscosity is 21.8mPas.
Embodiment 2: the preparation of hydrophobically modified associative thickener
The same embodiment 1 of the composition of emulsifying agent.
In preparatory emulsor, add 200.0g water; 2.5g emulsifying agent; Stir adding 101.5g MAA (being monomer A) down, 172.9g EA (being monomers B) and 0.60g linking agent DAP mixed solution and 33.0g SEM-25 (monomer C) obtain the 510.2g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 25.5g) of getting 360.0g water, 1.5g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in the 0.028g initiator A PS aqueous solution in the 1.0g water in advance.
Back 20 minutes of reaction beginning is added drop-wise to remaining 484.7.6g pre-emulsion (account for whole pre-emulsions 95%) and 0.03g initiator A PS solution constant speed in 3 hours of being dissolved in 100.0g water in the reactor drum again.Temperature of reaction remains on 85 ℃.After adding, pre-emulsion adds the 0.2g initiator A PS that is dissolved in advance in the 27.0g water again, insulation 1h.Make that SEM-25 accounts for A, B two monomer total amounts are the thickening material of 12.0wt%, its pH is 3.4, and the emulsion particle diameter is 130.0nm., adopt BrookfieldDV-II+Pro type rotational viscosimeter (following No. 3 rotors of room temperature, 60 rev/mins), recording emulsion viscosity is 18.8mPas.
Embodiment 3: the preparation of hydrophobically modified associative thickener
The composition of emulsifying agent: X 2073: OP-9: OP-21 mass ratio 2: 0.5: 1.5.
In preparatory emulsor, add 222.1g water, the 2.0g emulsifying agent stirs adding 109.7g MAA down, and 164.8g EA and 0.55g linking agent DAP mixed solution and 13.75g SEM-25 (monomer C) obtain the 512.g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 25.6g) of getting 360.0g water, 1.9g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in the 0.028g initiator ammonium persulfate aqueous solution in the 1.0g water in advance.
Back 25 minutes of reaction beginning is added drop-wise to remaining 486.4g pre-emulsion (all 95% of emulsions) and 0.03g initiator A PS solution constant speed in 3 hours of being dissolved in 95.5g water in the reactor drum again.Temperature of reaction remains on 85 ℃.After adding, pre-emulsion adds the 0.1g initiator A PS that is dissolved in advance in the 12.0g water again, insulation 1h.Make that SEM-25 accounts for A, B two monomer total amounts are the thickening material (T50 in table 1～4) of 5.0wt%, its pH is 3.1, and the emulsion particle diameter is 118nm., adopting Brookfield DV-II+Pro type rotational viscosimeter, following No. 3 rotors of room temperature record emulsion viscosity under 60 rev/mins of conditions be 21.7mPas.
Embodiment 4: the preparation of hydrophobically modified associative thickener
Emulsifying agent consist of X 2073: OP-21 mass ratio 1: 1.
In preparatory emulsor, add 220.1g water, the 2.0g emulsifying agent stirs adding 109.7g MAA down, and 164.8g EA and 0.6g linking agent DAP mixed solution and 4.4g SEM-25 obtain the 499.5g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 25g) of getting 360.0g water, 1.9g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in the 0.028g initiator ammonium persulfate aqueous solution in the 2.0g water in advance.
The reaction beginning was added drop-wise to remaining 474.5g pre-emulsion and the 0.03g initiator A PS solution constant speed in 3 hours that is dissolved in 95.5g water in the reactor drum in back 20 minutes again.Temperature of reaction remains on 85 ℃.After adding, pre-emulsion adds the 0.1g initiator A PS that is dissolved in advance in the 12.0g water again, insulation 1h.Make that SEM-25 accounts for A, B two monomer total amounts are the thickening material (T16 in table 1～4) of 1.6wt%, its pH is 2.8, and the emulsion particle diameter is 117nm., adopting Brookfield DV-II+Pro type rotational viscosimeter, recording emulsion viscosity under 60 rev/mins of conditions of following No. 3 rotors of room temperature is 18.0mPas.
Embodiment 5: the preparation of hydrophobically modified associative thickener
The same embodiment 3 of the composition of emulsifying agent.
In preparatory emulsor, add 222.1g water, the 2.0g emulsifying agent stirs adding 109.7g MAA down, and 164.8g EA and 0.55g linking agent DAP mixed solution and 3.02g SEM-25 (monomer C) obtain the 500.2g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 25g) of getting 355.5g water, 1.9g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in the 0.028g initiator ammonium persulfate aqueous solution in the 1.0g water in advance.
Back 25 minutes of reaction beginning is added drop-wise to remaining 475.2g pre-emulsion (all 95% of emulsions) and 0.03g initiator A PS solution constant speed in 3 hours of being dissolved in 100g water in the reactor drum again.Temperature of reaction remains on 85 ℃.After adding, pre-emulsion adds the 0.1g initiator A PS that is dissolved in advance in the 12.0g water again, insulation 1h.Make that SEM-25 accounts for A, B two monomer total amounts are the thickening material (T11 in table 1～4) of 1.1wt%, its pH is 2.5, and the emulsion particle diameter is 116nm., adopting Brookfield DV-II+Pro type rotational viscosimeter, following No. 3 rotors of room temperature record emulsion viscosity under 60 rev/mins of conditions be 16.7mPas.
According to the method for embodiment 1～5, can prepare monomer A, different, the different hydrophobically modified thickening material of SEM-25 content of B content.
Embodiment 6: controlled trial
The same embodiment 1 of the composition of emulsifying agent.
In preparatory emulsor, add 220.0g water, the 2.0g emulsifying agent stirs adding 123.0g MAA (methylacrylic acid down; Monomer A); 184.5g EA (ethyl propenoate, monomers B) and 0.62g linking agent DAP obtain the 530.1g pre-emulsion after stirring 30 minutes under 800 rev/mins.
The pre-emulsion (about 26.5g) of getting 360.0g water, 1.9g emulsifying agent and 1/20 then joins in the reactor drum, and keeping stirring velocity is 200 rev/mins, is warming up to 85 ℃, adds then to be dissolved in the 0.028g initiator ammonium persulfate aqueous solution in the 3.0g water in advance.
Back 20 minutes of reaction beginning is added drop-wise to remaining 503.6g pre-emulsion (all 95% of emulsions) and 0.03g initiator A PS solution constant speed in 3 hours of being dissolved in 95.0g water in the reactor drum again.Temperature of reaction remains on 85 ℃.Add the 0.1g initiator A PS that is dissolved in advance in the 12.5g water after pre-emulsion adds again, be incubated 1 hour.Make the coventional type thickening material (T00 in table 1～4) that does not contain SEM-25, its pH is 2.44, and the emulsion particle diameter is 78.4nm., using Brookfield DV-II+Pro type rotational viscosimeter, following No. 3 rotors of room temperature record emulsion viscosity under 60 rev/mins of conditions be 5.0mPas.
Embodiment 7: to the application of water-borne coatings
Getting solid content is 25% benzene emulsion; To wherein adding 1.0% to 2.5% the embodiment 1,3 account for benzene emulsion polymer solids quality and 6 thickening material respectively; Transfer pH to 7.4 with 1mol/L NaOH solution; Adopt Brookfield DV-II+Pro type rotational viscosimeter, use No. 3 rotors under 30 rev/mins of room temperatures, to measure its viscosity, the viscosity of emulsion is seen table 5 after the thickening.Obviously, when when benzene emulsion adds 1.5% thickening material of the present invention, its thickening effectiveness just begins to be superior to the thickening material (embodiment 6) of non-modified, and thickening effectiveness is more obvious with the increase of thickening material content in system.
Viscosity after the thickening of table 5 benzene emulsion is with the variation of thickening material addition
Claims (10)
1. hydrophobic modified associative thickener is characterized in that it being to be made through the free-radical emulsion polymerization method by following three kinds of monomers:
A. unsaturated carboxylic acid monomer is selected from methylene-succinic acid, butene dioic acid, acrylic or methacrylic acid;
B. carboxy-containing acid group's monoethylenically unsaturated monomer not is selected from vinylbenzene, vinyl acetic monomer, methyl acrylate, ethyl propenoate, propyl acrylate or methacrylic ester;
C. the unsaturated amphipathic function monomer of olefinic, be selected from polyethoxye (20) methylacrylic acid stearyl, polyethoxye (25) methylacrylic acid mountain Yu base ester, stearyl polyethoxye (10) allyl ethers, gather (methyl) vinylformic acid (terepthaloyl moietie) ester, gather (terepthaloyl moietie) monomethyl ether (methyl) propenoate, ROHM (terepthaloyl moietie) ester with gather (terepthaloyl moietie) monomethyl ether mono acrylic ester or triphenyl ethyl phenoxy polyethoxye (25) ether metacrylic acid ester;
More than three types of monomeric mass parts following: C.15～45 part B.130～190 part A.80～120 part,,, the solid content of gained thickening material is 28～32wt%.
2. hydrophobic modified associative thickener as claimed in claim 1 is characterized in that said monomer A is acrylic or methacrylic acid.
3. hydrophobic modified associative thickener as claimed in claim 1 is characterized in that said monomers B is an ethyl propenoate.
4. hydrophobic modified associative thickener as claimed in claim 1 is characterized in that said monomer C is triphenyl ethyl phenoxy polyethoxye (a 25) ether metacrylic acid ester, is called for short SEM-25, and structural formula is as shown in the formula I:
。
5. the preparation method of the described hydrophobic modified associative property thickening material of claim 1 adopts emulsion polymerization, comprises the steps:
(1) 200～280 parts of water and 1.5～2 parts of emulsifying agents are added in the preparatory emulsor; Stir adding monomer A monomers B and the mixed solution of monomer C and the linking agent that accounts for these three kinds of monomer total mass 0.05%-0.5% down, after stirring 30-40min under the 600-800 rev/min of stir speed (S.S.), obtaining pre-emulsion;
(2) 1/20 of the pre-emulsion that makes in 300～350 parts in water, 1.5～2 parts of emulsifying agents and the step (1) is added in the reactor drum; Under 150～200 rev/mins of stir speed (S.S.)s, stir; Be warming up to 75-90 ℃, add the aqueous solution that contains 0.025～0.035 part of initiator, wherein water is 0.5～1.0 part; Begin to react timing;
When (3) reaction is carried out 20-25 minute; Step (1) pre-emulsion with residual content is added drop-wise in the reactor drum with 0.35～0.45 part of initiator constant speed in 3 hours that is dissolved in 80～100 parts of water again; Add 0.05～0.10 part of initiator in 5～15 parts of water that is dissolved in for preparing after adding again; Be incubated 1-2 hour, promptly get thickening material.
6. the preparation method of hydrophobic modified associative property thickening material as claimed in claim 5; It is characterized in that used emulsifying agent is the combination of anionic emulsifier and nonionic emulsifier mass ratio 0.5～2.0; Wherein, Anionic emulsifier is X 2073 or sodium sulfate, and nonionic emulsifier is one of OP-9 or OP-21 or combination.
7. the preparation method of hydrophobic modified associative property thickening material as claimed in claim 6 is characterized in that used emulsifying agent is anionic emulsifier and 1: 1 combination of nonionic emulsifier mass ratio.
8. the preparation method of hydrophobic modified associative property thickening material as claimed in claim 5; It is characterized in that the said linking agent of step (1) is selected from Viscoat 295, Vinylstyrene, ethylene glycol diacrylate, glycol methacrylate or Phthalic acid, diallyl ester, the linking agent dosage accounts for monomer total mass 0.05%-0.5%.
9. the preparation method of hydrophobic modified associative property thickening material as claimed in claim 5 is characterized in that the said linking agent of step (1) is a Phthalic acid, diallyl ester, and the linking agent dosage accounts for the 0.1-0.3% of monomer total mass.
10. the application of the described hydrophobically modified associative thickener of claim 1, in use the pH of regulation system is to alkalescence, and the pH scope is 7.4-9.0.
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