CN1546542A - Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion - Google Patents
Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion Download PDFInfo
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- CN1546542A CN1546542A CNA2003101168016A CN200310116801A CN1546542A CN 1546542 A CN1546542 A CN 1546542A CN A2003101168016 A CNA2003101168016 A CN A2003101168016A CN 200310116801 A CN200310116801 A CN 200310116801A CN 1546542 A CN1546542 A CN 1546542A
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- vinyl monomer
- polymerization
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- 239000000839 emulsion Substances 0.000 title claims abstract description 28
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 12
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract 4
- 229910052710 silicon Inorganic materials 0.000 title claims abstract 4
- 239000010703 silicon Substances 0.000 title claims abstract 4
- 229920000058 polyacrylate Polymers 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 18
- -1 thiazolinyl cyclotetrasiloxane Chemical compound 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 229960000541 cetyl alcohol Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 14
- 229920000126 latex Polymers 0.000 description 14
- 229920002050 silicone resin Polymers 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPWXVNZFDXZIMS-UHFFFAOYSA-N 1-hydroxypropyl prop-2-enoate Chemical compound CCC(O)OC(=O)C=C CPWXVNZFDXZIMS-UHFFFAOYSA-N 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012703 microemulsion polymerization Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a process for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion with high organic silicon content (15%-25%), wherein the ring-opening polymerization of epoxy silane is carried out simultaneously with the free radical polymerization of vinyl monomer, i.e., (1) ring-opening polymerization occurs to epoxy silane at the presence of catalyst, and organic (ring) siloxane containing unsaturated bonds polycondensation is carried out, thus producing organosilicon resin and organosilicon resin containing unsaturated double bonds, (2) at the presence of initiating agent, the free radical polymerization of vinyl monomer is carried out, and in-situ graft polymerization of organosilicon resin containing unsaturated bonds is carried out to prepare organic silicon-g polyacrylic acid (ester) grafted copolymer (as compatiblizing agent).
Description
Technical field
The present invention relates to the preparation method of a kind of organic-silicon-modified polyacrylic acid (ester) emulsion (hereinafter to be referred as organosilicon crylic acid latex), the preparation method of the organosilicon crylic acid latex of particularly high organosilicon content (15%～25%).
Background technology
Vinylformic acid (ester) cold coating is 20th century coating new variety that grow up of the fifties.It has following advantage: look shallow, the transparency is fabulous, nondiscoloration, acidproof alkali salt, grease resistance etc.But also there are some shortcomings: as easy loss of gloss, low-temperature flexibility is relatively poor, water-permeable is more high.In order to remedy these shortcomings on vinylformic acid (ester) resin property, generally to carry out modification to vinylformic acid (ester) resin, the modification technology of vinylformic acid (ester) resin is main relevant with organosilicon.Coating is main chain with Si-O-Si with silicone resin, because the bond energy of Si-O key is greater than the bond energy of C-C key in the common organic polymer, therefore silicone resin has good thermotolerance, anti-ozone, resistance to UV aging, and, because surface tension is little, water and other pollutent are difficult for adhering to, so silicone resin has good moistureproofness, water resisting property and anti-steam etc.Have more excellent weathering resistance, gloss retention, resistance to chalking, anti-stain characteristic etc. through organic-silicon-modified vinylformic acid (ester) cold coating than unmodified vinylformic acid (ester) cold coating, be suitable for as the outdoor decoration building coating.
Prepare organic-silicon-modified polyacrylic acid (ester) emulsion, mainly be divided into cold spelling and chemical method.Cold spelling is simple to operate, is separated but be easy to generate two, and storage period is short.Chemical method generally is to carry out emulsion copolymerization with the organo-siloxane monomer and vinylformic acid (ester) monomer that contain vinyl group, but this siloxanes facile hydrolysis, influenced organosilyl activity, particularly when organic silicone content is big, can in emulsion polymerization process, produce a large amount of condensation products (even whole gelling), reaction can't be proceeded.Chemical method prepares another approach of organosilicon crylic acid latex, and when the silicone resin of band functional group existed, vinylformic acid (ester) monomer carried out letex polymerization, but the emulsion uniformity that this method obtains is poor.
Organosilicon content is less than 15% in organosilicon crylic acid latex, perhaps during the uniformity difference of emulsion and emulsion particle, organosilicon crylic acid latex can not represent its due various over-all propertieies well, so the synthetic relatively research topic of hot topic that remains now of organosilicon crylic acid latex: main research direction is organosilicon crylic acid latex preparation technology's the exploration preferably of high organosilicon content, uniformity.
Summary of the invention
The object of the present invention is to provide a kind of novel process of organosilicon crylic acid latex of synthetic high organosilicon content (15%～25%).
The preparation method of a kind of organic-silicon-modified polyacrylic acid of the present invention (ester) emulsion is a major ingredient with organosilane monomer and vinyl monomer, it is characterized in that preparation process may further comprise the steps successively:
(1) pre-emulsification: emulsifying agent, water soluble starter and catalyzer are put in the deionized water, after treating to dissolve fully, are added and be dissolved with oil-soluble initiator and auxiliary agent and organosilane monomer that mixes and vinyl monomer, stir pre-emulsion;
(2) polyreaction: emulsifying agent is put in the deionized water, add water soluble starter and catalyzer, after the dissolving, logical nitrogen 20 minutes is warmed up to 70～80 ℃ fully, began to drip pre-emulsion 2～5 hours, after being added dropwise to complete, being warming up to 85～100 ℃ and continuing reaction 2～5 hours, be cooled to 40 ℃, regulate pH to 7～8, filter;
Wherein organosilane monomer is epoxy silane and contains the monomeric mixture of vinyl organosilicon.
Described epoxy silane is an octamethylcyclotetrasiloxane, contains the vinyl organosilicon monomer and be in tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltriethoxysilane, the vinyltriethoxysilane one or more.
Described vinyl monomer is methacrylic acid and (C thereof
1～C
10) alcohol ester, vinylformic acid and (C thereof
1～C
10) in the alcohol ester, vinylbenzene one or more.
The weight ratio of used organosilane monomer and vinyl monomer is 2～30/98～70, is preferably 5～25/95～75.
Described emulsifying agent is the moon/nonionic compound emulsifier, and the ratio of the moon/nonionic emulsifying agent is 1: 0.25～5, and total consumption is 0.5～7% (accounting for the polymerization single polymerization monomer weight percent), and wherein the consumption of pre-emulsion process is 3/4～1/3 of whole consumptions.
Preferred, emulsifying agent is 2～4 kinds in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, polyoxyethylene nonyl phenyl Vinyl Ether, ethoxylated alkylphenol ammonium sulfate, the octylphenol polyethylene ethylene oxide ether.
Described water soluble starter is one or both of Potassium Persulphate, ammonium persulphate; Oil-soluble initiator is one or both in benzoyl peroxide, the Diisopropyl azodicarboxylate, total consumption is 0.3～1.5% (accounting for the weight percent of vinyl monomer), wherein oil-soluble initiator accounts for 0～50% of total consumption, and the consumption of pre-emulsion process is 3/4～1/3 of whole consumptions.
Described auxiliary agent is one or more in n-Hexadecane, cetyl alcohol, 1-amylalcohol, the polymethyl acrylate, and the total consumption of auxiliary agent is 0～5% (accounting for the polymerization single polymerization monomer weight percent).
The present invention is the preparation method of a kind of organic-silicon-modified polyacrylic acid (ester) emulsion, its polyreaction is undertaken by micro-emulsion polymerization mechanism, the ring-opening polymerization of epoxy silane and the radical polymerization of vinyl monomer is simultaneously carried out synchronously, that is: (1) ring-opening polymerization: epoxy silane ring-opening polymerization under the effect of catalyzer, with organic (ring) siloxanes polycondensation that contains unsaturated double-bond, generate silicone resin and the silicone resin that contains unsaturated link(age) simultaneously.(2) free-radical polymerized: under the initiator effect, radical polymerizable vinyl monomer, and and contain the silicone resin generation in-situ grafting polymerization of unsaturated link(age), generate organosilicon-g-polyacrylic acid (ester) graft copolymer (making compatilizer).
Characteristics of the present invention are: (1) has consistency preferably for making silicone resin and polymers of vinyl monomers, introduces unsaturated link(age) in the silicone resin molecular chain.When vinyl monomer generation Raolical polymerizable, just can with the organosilicon polymer generation in-situ grafting polymerization that contains unsaturated link(age), organosilicon-g-polyacrylic acid (ester) the graft copolymerization deposits yields of some amount is arranged.Graft copolymer is as compatilizer, thereby can improve the consistency of silicone resin and vinyl polymer.(2) adopt the micro-emulsion polymerization technology, reduce the diffusive migration of vinyl monomer in polymerization process to greatest extent, thereby polyreaction is occurred in the specific polymerization place (drop).Like this, because the generation of organosilicon-g-polyacrylic acid (ester) graft copolymer in specific polymerization place and the polymerization process, can obtain silicone resin and vinyl polymer intimate mixing and consistency latex particle preferably, therefore, emulsion has fabulous stably dispersing performance.(3) epoxy silane, the ring-opening polymerization of organic (ring) siloxanes that contains unsaturated link(age) and polycondensation and the monomeric radical polymerization of vinylformic acid (ester) class are carried out synchronously, this helps the uniformity in emulsion and the emulsion particle on the one hand, can simplify preparation technology on the other hand, shorten the production time, reduce cost.
Adopt the technology of the present invention to prepare organosilicon crylic acid latex in a word, there is not the uneven problem of emulsion system in the problem that does not exist silicone resin latex particle and vinyl polymer latex particle to be separated in polyreaction yet.Organosilicon content is 15%～25% in the emulsion, and solid content is greater than 40%.Filming of emulsion has very strong hydrophobicity.This synthesis route is simple and direct, be easy to control, production cost is lower, so the present invention has actual application prospect.
Embodiment
In order to illustrate that better the present invention, spy enumerate following embodiment, but the present invention is not limited in following embodiment.
Embodiment 1:
1) pre-emulsification: with the 0.8g sodium lauryl sulphate, 1.2g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 1.0g ethoxylated alkylphenol ammonium sulfate (RHODAPEX CO-436,58%), 0.25g Potassium Persulphate, 0.4g Witco 1298 Soft Acid is dissolved in the 130.0g deionized water, after stirring, with the 48.5g butyl acrylate, 48.5g methyl methacrylate, 1.5g vinylformic acid, 2.0g N hydroxymethyl acrylamide, 5.0g vinylformic acid α-hydroxypropyl acrylate, 18.5g octamethylcyclotetrasiloxane, 1.3g gamma-methyl allyl acyloxypropyl trimethoxysilane, 1.5g the mixture of cetyl alcohol adds, and stirs to such an extent that pre-emulsion is stand-by.
2) organosilicon crylic acid latex is synthetic: in the reaction flask that disposes thermometer, agitator, reflux exchanger and dropping funnel, 0.5g sodium lauryl sulphate, 0.6g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 0.5g ethoxylated alkylphenol ammonium sulfate (RHODAPEX CO-436), 0.3g Potassium Persulphate, 0.3g Witco 1298 Soft Acid are added in the 50g deionized water, stir, logical nitrogen is warmed up to 80 ℃ after 20 minutes, begin to drip pre-emulsion, drip in 3 hours, insulation is warmed up to 85 ℃ of reactions 3 hours after half an hour.Be cooled to 40 ℃, regulate pH to 7, filter.Can make solid content is 41.1%, the latex product of viscosity 12 seconds (being coated with-4 glasss).Emulsion is coated on the sheet glass, drying at room temperature 2 hours, what get final product transparently films.
The technological process of embodiment 2～5 is identical with example one, and raw material add-on and experimental result are listed in table 1 and the table 2.
Table 1
| The raw material add-on | Raw material | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Methyl methacrylate (g) | ????38.5 | ?????39.5 | ???61.5 | ????31.5 | |
| Butyl acrylate (g) | ????48.5 | ?????46.0 | ???36.5 | ????42.5 | |
| Vinylformic acid (g) | ????1.5 | ?????1.5 | ????1.5 | ????1.5 | |
| N hydroxymethyl acrylamide (g) | ????2.0 | ?????3.0 | ????4.0 | ????2.0 | |
| Vinylformic acid α-hydroxypropyl acrylate (g) | ????6.0 | ?????4.0 | ????3.0 | ????4.0 | |
| Vinylbenzene (g) | ????10.0 | ?????6.5 | ????12.0 | ||
| Octamethylcyclotetrasiloxane (g) | ????18.5 | ?????24.5 | ???18.5 | ????31.5 | |
| Tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (g) | ?????1.1 | ????1.3 | |||
| Gamma-methyl allyl acyloxypropyl trimethoxysilane (g) | ????1.3 | ????1.5 | |||
| Dodecyl sulphate (g) | ????1.2 | ????0.7 | |||
| Witco 1298 Soft Acid (g) | ?????0.9 | ????1.5 | |||
| Sodium lauryl sulphate (g) | ????1.0 | ????0.8 | |||
| Sodium dodecylbenzene sulfonate (g) | ?????0.9 | ????0.6 | |||
| Polyoxyethylene nonyl phenyl vinyl ether (OP-10) (g) | ????2.0 | ?????2.8 | ????1.6 | ????1.0 | |
| Ethoxylated alkylphenol ammonium sulfate (58%) (g) | ????1.0 | ?????0.6 | ????1.5 | ????2.5 | |
| Potassium Persulphate (g) | ????0.42 | ?????0.35 | ????0.28 | ????0.46 | |
| Deionized water (g) | ????180.0 | ?????180.0 | ????180.0 | ????180.0 | |
| Reaction conditions | Pre-emulsion drips the time (h) | ????3 | ?????3 | ????3 | ????3 |
| The pre-emulsion dropping temperature (℃) | ????80 | ?????85 | ????75 | ????80 | |
| Polymeric reaction temperature (℃) | ????85 | ?????90 | ????85 | ????95 | |
| Polymerization reaction time (h) | ????3 | ?????2.5 | ????3.5 | ????2 |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Solid content (%) | ????41.1 | ????42.1 | ????40.7 | ????41.8 | ????40.3 |
| Gel content (oven dry back) (%) | ????0.18 | ????0.08 | ????0.11 | ????0.06 | ????0.15 |
| Emulsion particle median size (nm) | ????121 | ????157 | ????187 | ?????153 | ????146 |
| Organosilicon content (%) | ????15.8 | ????15.6 | ????20.3 | ????15.8 | ????25.2 |
| The pH value | ????7.0 | ????7.0 | ????7.0 | ?????7.0 | ????7.0 |
| Viscosity (being coated with-4 glasss/second) | ????12.00 | ????12.69 | ????15.11 | ????13.52 | ????15.36 |
| Calcium ion stability (5%CaCl 2) | By | By | By | By | By |
| Mechanical stability (4000 change) | 30min passes through | 30min passes through | 30min passes through | 30min passes through | 30min passes through |
| Freeze-thaw stability (5 ℃) | 3 cycle through | 3 cycle through | 3 cycle through | 3 cycle through | 3 cycle through |
| Stability in storage (year) | ????0.5 | ????0.5 | ????0.5 | ?????0.5 | ????0.5 |
| Dilution stability | By | By | By | By | By |
Claims (9)
1, the preparation method of a kind of organic-silicon-modified polyacrylic acid (ester) emulsion is a major ingredient with organosilane monomer and vinyl monomer, it is characterized in that preparation process may further comprise the steps successively:
(1) pre-emulsification: emulsifying agent, water soluble starter and catalyzer are put in the deionized water, after treating to dissolve fully, are added and be dissolved with oil-soluble initiator and auxiliary agent and organosilane monomer that mixes and vinyl monomer, stir pre-emulsion;
(2) polyreaction: emulsifying agent is put in the deionized water, add water soluble starter and catalyzer, after the dissolving, logical nitrogen 20 minutes is warmed up to 70～80 ℃ fully, began to drip pre-emulsion 2～5 hours, after being added dropwise to complete, being warming up to 85～100 ℃ and continuing reaction 2～5 hours, be cooled to 40 ℃, regulate pH to 7～8, filter;
Wherein organosilane monomer is epoxy silane and contains the monomeric mixture of vinyl organosilicon.
2, according to the described preparation method of claim 1, it is characterized in that described epoxy silane is an octamethylcyclotetrasiloxane, contain the vinyl organosilicon monomer and be in tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltriethoxysilane, the vinyltriethoxysilane one or more.
Described vinyl monomer is methacrylic acid and (C thereof
1～C
10) alcohol ester, vinylformic acid and (C thereof
1～C
10) in the alcohol ester, vinylbenzene one or more.
3, according to the described preparation method of claim 1, the weight ratio that it is characterized in that organosilane monomer and vinyl monomer is 2～30: 98～70.
4, according to the described preparation method of claim 1, the weight ratio that it is characterized in that organosilane monomer and vinyl monomer is 5～25: 95～75.
5, according to the described preparation method of claim 1, it is characterized in that described emulsifying agent is the moon/nonionic compound emulsifier, the ratio of the moon/nonionic emulsifying agent is 1: 0.25～5, total consumption is 0.5～7% (accounting for the polymerization single polymerization monomer weight percent), and wherein the consumption of pre-emulsion process is 3/4～1/3 of whole consumptions.
6,, it is characterized in that described emulsifying agent is 2～4 kinds in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, polyoxyethylene nonyl phenyl Vinyl Ether, ethoxylated alkylphenol ammonium sulfate, the octylphenol polyethylene ethylene oxide ether according to the described preparation method of claim 5.
7,, it is characterized in that described water soluble starter is one or both of Potassium Persulphate, ammonium persulphate according to the described preparation method of claim 1; Oil-soluble initiator is one or both in benzoyl peroxide, the Diisopropyl azodicarboxylate, total consumption is 0.3～1.5% (accounting for the weight percent of vinyl monomer), wherein oil-soluble initiator accounts for 0～50% of total consumption, and the consumption of pre-emulsion process is 3/4～1/3 of whole consumptions.
8, according to the described preparation method of claim 1, it is characterized in that described catalyzer is one or more of Witco 1298 Soft Acid, dodecyl sodium sulfonate, dodecyl sulphate, tosic acid, total consumption was 0.5～10% (occupying machine silicon monomer weight percent), and wherein the consumption of pre-emulsion process is 3/4～1/3 of whole consumptions.
9, according to the described preparation method of claim 1, it is characterized in that described auxiliary agent is one or more in n-Hexadecane, cetyl alcohol, 1-amylalcohol, the polymethyl acrylate, the total consumption of auxiliary agent is 0～5% (accounting for the polymerization single polymerization monomer weight percent).
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