CN1607233A - Process for polymerization of aqueous acrylate paint - Google Patents
Process for polymerization of aqueous acrylate paint Download PDFInfo
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- CN1607233A CN1607233A CN 200310100342 CN200310100342A CN1607233A CN 1607233 A CN1607233 A CN 1607233A CN 200310100342 CN200310100342 CN 200310100342 CN 200310100342 A CN200310100342 A CN 200310100342A CN 1607233 A CN1607233 A CN 1607233A
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- 239000003973 paint Substances 0.000 title claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 title abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 19
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims abstract description 5
- 239000000872 buffer Substances 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- -1 acyloxy silanes Chemical class 0.000 claims description 17
- 239000004971 Cross linker Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 238000007599 discharging Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000007686 potassium Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 26
- 239000000839 emulsion Substances 0.000 abstract description 25
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000004816 latex Substances 0.000 abstract 1
- 229920000126 latex Polymers 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 125000005375 organosiloxane group Chemical group 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229960000878 docusate sodium Drugs 0.000 description 4
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
A polymerizing method for water paint, especially for raising property of acr water paint. The process is that, dripping monomer and initiator into emulsifier aqueous solution having part of initiator, hard monomer, pH value buffer to react, dripping soft monomer continuing heat insulation reaction, adding siloxane crosslinking agent, keeping pH value in definite range to forming protection to siloxane, so making organic siloxane presence stable in emulsion using water as medium and mainly distributed on latex surface in forming film to raise film forming crosslinking degree. Said invention provides a simple process, fine film property and performance improved method.
Description
Technical field:
The present invention relates to a kind of polymerization process of water-borne coatings, particularly improve the polymerization process of acrylic ester aquosity coating property.
Background technology:
Water soluble acrylic acid lipin polymer emulsion has good weathering resistance, resistance to acids and bases, polluting proofing property, performance such as environmentally friendly, has become a kind of important coating variety.But defective such as there is the film-forming temperature height in pure third, phenylpropyl alcohol coating, not high, the anti-after tackiness of the physical strength of filming is not good, only by introducing function monomer, or to carry out modification by means such as core-shell emulsion polymerization and soap-free polymerizations be to satisfy more and more higher application requiring.Therefore people have carried out a large amount of research to emulsion that can room temperature film-forming, as: US 4772680 is by acetoacetyl and the normal temperature crosslinked emulsion of ketoimine reaction acquisition.US 6538062 utilizes the material and the hydrazides that contain active carbonyl to react the room temperature crosslinking curing of realizing coating.The siloxanes of EP 1210834 usefulness special constructions is hydrolyzed into the normal temperature crosslinked coating of silanol condensation prepared.Because the Si-O bond energy is big, to light, thermally-stabilised, is not subject to action of ultraviolet light, therefore use organo-siloxane as cross-linking monomer, make coating in self-vulcanizing, can improve the weathering resistance of coating, high-and low-temperature resistance, water tolerance, performances such as hardness.Though vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three common unsaturated organosilicon oxygen alkane such as ('beta '-methoxy Ethoxysilanes) can be applied in and improve solution property in the solution polymerization, but because siloxanes facile hydrolysis, produce a large amount of condensation products, and make polyreaction can't carry out at aqueous phase, therefore the application that improves emulsion property with the organo-siloxane that contains unsaturated group and other organosilane monomer direct polymerization is also seldom.JP51-146525, though JP54-3512 with the organo-siloxane that contains unsaturated group and other organosilane monomer direct polymerization, stability of emulsion is poor, separates, condenses.CN1217360A; CN1217360A protects organo-siloxane with the hydroxyl polysiloxane; this method is the synthesis of hydroxy polysiloxane at first; add in the polymerization system again; hydroxyl siloxanes and organo-siloxane carry out graft reaction; be used for protecting not hydrolysis of organo-siloxane, the siloxanes after the grafting improves the performance of emulsion, complex process as linking agent.In addition, in the present emulsion polymerization technique, linking agent often adds when dripping monomer or pre-emulsification, and partial cross-linked dose is enclosed in emulsion particle inside, to crosslinked not contribution between particle; So just reduced the probability that linking agent is distributed in the emulsion particle surface, not only dosage of crosslinking agent is big, and the degree of crosslinking of the film during the build-up of particles film forming reduces relatively.
Summary of the invention:
The technical problem to be solved in the present invention: make organo-siloxane stable existence in the emulsion that with water is medium, and when film forming, mainly be distributed in the emulsion particle surface, improve film forming degree of crosslinking, a kind of technology is simple, film properties good thereby provide, and the direct crosslinking polymerization of organo-siloxane improves the polymerization process of emulsion property.
Main technical schemes: main points of the present invention are: making organo-siloxane by the control reacting system PH value is stable existence in the emulsion of medium at water, and in emulsion drying and forming-film process again hydrolytic condensation make film crosslinked; Characteristics at the organo-siloxane cross-linking system; adjust hard monomer; the adding process sequence of soft monomer and linking agent; improve the film forming properties of coating; main technique is: with hard monomer; initiator is added drop-wise to and contains the part initiator; hard monomer; in the emulsifier aqueous solution of pH value buffer reagent; under 50-90 ℃; reacted at least 30 minutes; drip soft monomer and continue insulation reaction, in system, add siloxane crosslinker, react after at least 0.5 hour; carry out the back and eliminate initiation reaction; add the pH value conditioning agent in the reaction, make pH value remain at the 6-8 scope, so that siloxanes is formed protection; system cools to room temperature, filters discharging.
Above-mentioned siloxane crosslinker is selected from: the mixture of one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy Ethoxysilane), vinyl three tert.-butoxy silane, vinyl three acyloxy silanes, consumption is 0.25%～10% of a vinyl monomer.
Mentioned emulsifier can be anionic or non-ionic type, it also can be the compound use of anionic/non-ionic type, strengthen the consumption of emulsifying agent, can make emulsion more stable, and can reduce the particle diameter of particle, but the introducing of emulsifying agent makes the wetting ability of film strengthen, and water tolerance significantly descends, so the consumption of emulsifying agent accounts for monomeric 1%～5%.
What above-mentioned initiator was selected from: Potassium Persulphate, ammonium persulphate, Potassium Persulphate---sodium bisulfite, ammonium persulphate---in the sodium bisulfite is a kind of.It is rongalite---tertbutyl peroxide that initiator is eliminated in the back.The consumption of initiator is 1 ‰～1% of a vinyl monomer consumption.
Above-mentioned PH conditioning agent is selected from: a kind of in sodium bicarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC.
Effect of the present invention: present method is directly participated in reaction as linking agent with siloxanes, and with the method that pH value is regulated, it is stable to make that siloxane crosslinker remains, and simplifies polymerization technique, reduces cost.
The reaction later stage adds siloxane crosslinker, linking agent has the surface of bigger Probability Distribution at emulsion particle, makes the more siloxanes can hydrolytic condensation when film forming, the reticulated structure of formation, improve the degree of crosslinking of film, thereby improved the performance such as water tolerance, hardness of film.
Add hard monomer during reaction earlier and can guarantee that film has certain rigidity, the back adds soft monomer, can be when suitably reducing the soft monomer consumption, guarantee that emulsion can film forming in lower temperature, and make film that certain snappiness be arranged, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming.
Embodiment:
A) hard monomer, initiator are added drop-wise in the emulsifier aqueous solution that contains part initiator, hard monomer, pH value buffer reagent, under 50-90 ℃, react; Wherein hard monomer is selected from: one or more in methyl methacrylate, isobornyl methacrylate, vinylbenzene, vinyl cyanide, the glycidyl methacrylate; Emulsifying agent can be anionic, non-ionic type, also can be the compound use of anionic/non-ionic type, and consumption is 1%～5% of a vinyl monomer.Wherein anionic emulsifier is selected from: one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, ethoxylated alkylphenol sulfuric acid amine, alkyl oxy DAADBSA disodium, the dioctyl disodium sulfosuccinate; Nonionic emulsifier is selected from: one or more in octylphenol ethoxylate, a basic phenol ethoxylate, the polyoxyethylene sorbitan carboxylic ester.Increase the consumption of emulsifying agent, can make emulsion more stable, and can reduce the particle diameter of particle, but the introducing of emulsifying agent makes the wetting ability of film strengthen that water tolerance significantly descends, so the consumption of emulsifying agent is good in 1%～3% (referring to account for monomer).
B) hard monomer dropwises, and reacts after at least 30 minutes, drips soft monomer and continues insulation reaction 1.5-2 hour; Soft monomer is selected from: one or more in methyl acrylate, ethyl propenoate, butyl acrylate, the Isooctyl acrylate monomer; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming.
C) in system, add siloxane crosslinker; After reacting about 0.5 hour, carry out the back and eliminate initiation reaction.In the reaction, surveyed a pH value, keep pH value in 6～8 scope every 30 minutes.Wherein, siloxane crosslinker is selected from: the mixture of one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy Ethoxysilane), vinyl three tert.-butoxy silane, vinyl three acyloxy silanes, consumption is 0.25%～10% of a vinyl monomer.Because the siloxane crosslinker facile hydrolysis, and price is expensive, and therefore under the situation that can reach than low cross-linking agent consumption than high-crosslinking-degree, the consumption of 1%～3% (refer to account for monomeric) is good.
What initiator was selected from: Potassium Persulphate, ammonium persulphate, Potassium Persulphate---sodium bisulfite, ammonium persulphate---in the sodium bisulfite is a kind of.It is rongalite---tertbutyl peroxide that initiator is eliminated in the back.The consumption of initiator is 1 ‰～1% of a vinyl monomer consumption.The PH conditioning agent is selected from: a kind of in sodium bicarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC.
E) eliminated after 1 hour the back, and system cools to room temperature, regulates PH more than or equal to after 8, filters discharging.
Embodiment
Embodiment 1: the water that adds 110 grams in the four-hole bottle that has water of condensation, stirring, thermometer, Dropping feeder, 1.4 gram dioctyl disodium sulfosuccinate, 0.21 gram sodium bicarbonate, logical nitrogen, be heated to 50 ℃, drip 42 gram methyl methacrylates, 35 gram vinylbenzene, 0.14 gram sodium bisulfite (being dissolved in the 45 gram water), 0.31 gram ammonium persulphate (being dissolved in the 45 gram water) begins to drip 63 gram butyl acrylates after about 1 hour.Dropwise reaction after 1 hour at butyl acrylate, added 0.35 gram vinyl three ('beta '-methoxy Ethoxysilane) back insulation reaction 2 hours, be warmed up to 75 ℃ of reactions 1 hour afterwards.Drop to room temperature Deng system temperature, regulate pH value to 8---9, filter the back discharging.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 2: the consumption of vinyl three among the embodiment 1 ('beta '-methoxy Ethoxysilane) is increased to 1.4 grams.All the other conditions are identical with embodiment 1.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1, table 3, table 4.
Embodiment 3: the consumption of vinyl three among the embodiment 1 ('beta '-methoxy Ethoxysilane) is increased to 4.2 grams, and all the other conditions are identical with embodiment 1.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 4: change 0.35 gram vinyl three ('beta '-methoxy Ethoxysilane) among the embodiment 1 into 7 gram vinyl, three tert.-butoxy silane/7 gram vinyltrimethoxy silanes.All the other conditions are identical with embodiment 1.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 5-8: change the vinyl among the embodiment 1-4 three ('beta '-methoxy Ethoxysilane) into vinyltrimethoxy silane respectively.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 2.
Embodiment 9: change the initiator among the embodiment 2 (0.14 gram sodium bisulfite, 0.31 gram ammonium persulphate) into 1.40 gram ammonium persulphates.And reaction is carried out at 90 ℃ all the time.All the other conditions are identical with embodiment 1.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 10: change 42 gram methyl methacrylates, the cinnamic hard monomer of 35 grams among the embodiment 2 into 7.79 gram methyl isobornyl thiocyanoacetates, 55.1 gram methyl methacrylate, 31.5 gram vinylbenzene, change soft monomer into 7.79 gram Isooctyl acrylate monomers by 63 gram butyl acrylates, 55.1 gram butyl acrylates.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 11-14: change the gram of 1.4 among the embodiment 2 dioctyl disodium sulfosuccinate into 0.7 gram dioctyl disodium sulfosuccinate, 4.2 gram dioctyl disodium sulfosuccinates respectively, 4.2 gram Sodium dodecylbenzene sulfonate/2.8 gram polyoxyethylene sorbitan carboxylic esters, all the other conditions are identical with embodiment 1.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 15: change the adding mode of siloxane crosslinker among the embodiment 2 into after methyl methacrylate/vinylbenzene mixes dropping.All the other conditions are identical with embodiment 2.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 3.
Embodiment 16: the styrene/methacrylic acid methyl esters/siloxane crosslinker among the embodiment 2 and the aqueous solution of emulsifying agent are stirred in advance, carry out pre-emulsification, change and drip pre-emulsion.All the other conditions are identical with embodiment 2.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 3.
Embodiment 17: do not add sodium bisulfite among the embodiment 2, all the other conditions are identical with embodiment 2.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 4.
Table 1
| Polymerization stability | Degree of crosslinking | Water tolerance (90 ℃ of water temperatures) | Water tolerance (20 ℃ of water temperatures) | |
| [embodiment 1] | Gel-free, polymerization-stable | ?36.5％ | Turn white | By |
| [embodiment 2] | Gel-free, polymerization-stable | ?79.6％ | By | By |
| [embodiment 3] | Gel-free, polymerization-stable | ?89.4％ | By | By |
| [embodiment 4] | Small amount of gel is arranged | ?94.3％ | By | By |
| [embodiment 9] | Gel-free, polymerization-stable | ?77.8％ | By | By |
| [embodiment 10] | Gel-free, polymerization-stable | ?76.4％ | By | By |
| [embodiment 11] | Gel-free, polymerization-stable | ?80.2％ | By | By |
| [embodiment 12] | Gel-free, polymerization-stable | ?79.4％ | By | By |
| [embodiment 13] | Gel-free, polymerization-stable | ???81.0％ | By | By |
| [embodiment 14] | Gel-free, polymerization-stable | ???77.5％ | By | By |
Table 2
| Polymerization stability | Degree of crosslinking | Water tolerance (90 ℃ of water temperatures) | Water tolerance (20 ℃ of water temperatures) | |
| [embodiment 5] | Gel-free, polymerization-stable | ???34.6％ | Turn white | By |
| [embodiment 6] | Gel-free, polymerization-stable | ???75.2％ | By | By |
| [embodiment 7] | Gel-free, polymerization-stable | ???87.3％ | By | By |
| [embodiment 8] | Small amount of gel is arranged | ???95.6％ | By | By |
Table 3
| Polymerization stability | Degree of crosslinking | Water tolerance (90 ℃ of water temperatures) | Water tolerance (20 ℃ of water temperatures) | |
| [embodiment 2] | Gel-free, polymerization-stable | ??79.60％ | By | By |
| [embodiment 15] | Gel-free, polymerization-stable | ??49.20％ | Turn white | Turn white |
| [embodiment 16] | Gel-free, polymerization-stable | ??43.10％ | Turn white | Turn white |
Table 4
| Reaction times (hour) | ??0 | ??0.5 | ?1 | ????1.5 | ??2 | ????2.5 | ????3 | ??3.5 | ????4 | ??4.5 | |
| [embodiment 2] | PH value | ??7 | ??7 | ?6.8 | ????6.5 | ??6.5 | ????6.5 | ????6.5 | ??6.4 | ??6.4 | ??6.4 |
| Emulsion state | Normally | Normally | Normally | Normally | Normally | Normally | Normally | Normally | Normally | Normally | |
| [embodiment 17] | PH value | ??7 | ??6.7 | ?6.2 | ????5.1 | ??4.1 | ????3.7 | ????/ | ????/ | ?????/ | |
| Emulsion state | Normally | Normally | Normally | The emulsion wall built-up begins to have material to separate out | Obviously there is solid to separate out | A large amount of solids are separated out, and the system that has a strong impact on stirs | Can't normally stir, can't continue reaction | ????/ | ????/ | ????/ |
Above-mentioned polymerization system stability test method: observe the letex polymerization phenomenon, emulsion appearance after polyreaction finishes, filters with 400 order steel meshes, and filter residue is weighed, and calculates filter residue and accounts for monomeric per-cent, carries out relatively.
The mensuration of degree of crosslinking: take by weighing a certain amount of film that in baking oven, dries to constant weight, pack in the load weighted in advance filter paper, in cable type extractor according, use acetone extracting 48 hours, film after the extracting is dried to constant weight in baking oven, be calculated as follows the degree of crosslinking of film: film quality (g) * 100% before quality (the g)/extracting of film degree of crosslinking=extracting caudacoria.
The water resistance test of film: GB/T1733-93 tests according to GB.
Claims (5)
1, a kind of polymerization process of water soluble acrylic acid ester paint, containing hard monomer, soft monomer, initiated polymerization in the initiator system of siloxane crosslinker, it is characterized in that: with hard monomer, initiator is added drop-wise to and contains the part initiator, hard monomer, in the emulsifier aqueous solution of pH value buffer reagent, under 50-90 ℃, reacted at least 30 minutes, drip soft monomer and continue insulation reaction, in system, add siloxane crosslinker, react after at least 0.5 hour, carry out the back and eliminate initiation reaction, add the pH value conditioning agent in the reaction, make pH value remain at the 6-8 scope, system cools to room temperature, and pH value filters discharging greater than 8.
2, polymerization process according to claim 1, it is characterized in that: described siloxane crosslinker is selected from: the mixture of one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy Ethoxysilane), vinyl three tert.-butoxy silane, vinyl three acyloxy silanes, consumption is 0.25%～10% of a vinyl monomer.
3, polymerization process according to claim 1 is characterized in that: described emulsifying agent is that anionic, non-ionic type or anionic/non-ionic type are compound, and the consumption of emulsifying agent accounts for monomeric 1%～5%.
4, polymerization process according to claim 1, it is characterized in that: described initiator is selected from: Potassium Persulphate, ammonium persulphate, Potassium Persulphate---sodium bisulfite, ammonium persulphate---sodium bisulfite a kind of, it is rongalite---tertbutyl peroxide that initiator is eliminated in the back, and the consumption of initiator is 1 ‰～1% of a vinyl monomer consumption.
5, polymerization process according to claim 1 is characterized in that: described PH conditioning agent is selected from: a kind of in sodium bicarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC.
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| CN101817906A (en) * | 2010-04-23 | 2010-09-01 | 北京化工大学 | Aqueous acrylic acid series wooden ware sealing paint and method for preparing special emulsion thereof |
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| CN106543333B (en) * | 2016-10-27 | 2020-03-03 | 万华化学集团股份有限公司 | High-corrosion-resistance acrylic emulsion, preparation method thereof and water-based acrylic anticorrosive paint |
| CN111909318A (en) * | 2020-08-21 | 2020-11-10 | 万华化学集团股份有限公司 | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application |
| CN111909318B (en) * | 2020-08-21 | 2022-07-12 | 万华化学集团股份有限公司 | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application |
| CN115124900A (en) * | 2022-07-27 | 2022-09-30 | 厦门双瑞船舶涂料有限公司 | IBOA modified long-acting anticorrosion water-based acrylic coating and preparation method thereof |
| CN117384526A (en) * | 2023-11-29 | 2024-01-12 | 佛山市耐高建材有限公司 | Waterproof coating and preparation method thereof |
| CN117384526B (en) * | 2023-11-29 | 2024-04-02 | 佛山市耐高建材有限公司 | Waterproof coating and preparation method thereof |
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