CN102516448A - Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method - Google Patents
Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method Download PDFInfo
- Publication number
- CN102516448A CN102516448A CN201110434369XA CN201110434369A CN102516448A CN 102516448 A CN102516448 A CN 102516448A CN 201110434369X A CN201110434369X A CN 201110434369XA CN 201110434369 A CN201110434369 A CN 201110434369A CN 102516448 A CN102516448 A CN 102516448A
- Authority
- CN
- China
- Prior art keywords
- copolymer emulsion
- reactive emulsifier
- emulsifier
- acrylate copolymer
- silicon acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 62
- 239000000839 emulsion Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920001577 copolymer Polymers 0.000 title claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 14
- 239000011737 fluorine Substances 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 37
- -1 Acrylic ester Chemical class 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 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 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001282 organosilanes Chemical class 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 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
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000002512 suppressor factor Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 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 claims description 2
- PPWMOFIQJFERGS-UHFFFAOYSA-N 2-(4,4,4-trifluorobutan-2-yl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC(CC(F)(F)F)[SiH]1O[SiH2]O[SiH2]O1 PPWMOFIQJFERGS-UHFFFAOYSA-N 0.000 claims description 2
- JGWUKKFNKOUBPW-UHFFFAOYSA-N 2-ethenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 JGWUKKFNKOUBPW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 5
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- JGHTXIKECBJCFI-UHFFFAOYSA-N trifluoro(propyl)silane Chemical compound CCC[Si](F)(F)F JGHTXIKECBJCFI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RHDSWVLEZOIOBB-UHFFFAOYSA-N OC(=O)[C]F Chemical compound OC(=O)[C]F RHDSWVLEZOIOBB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004094 surface-active agent Substances 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-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UREOZNJAZZUPGJ-UHFFFAOYSA-N ethenyl(triethoxy)silane silane Chemical compound [SiH4].CCO[Si](OCC)(OCC)C=C UREOZNJAZZUPGJ-UHFFFAOYSA-N 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a fluorine-containing silicon acrylate copolymer emulsion prepared by using a reactive emulsifier and a method thereof. The reaction is completed in one step, the process is simple, the reaction condition is mild, and the industrial production is easy to realize; the adopted raw materials are all the raw materials which are widely used in the industry at present and are cheap and easy to obtain; a complex system of a reactive emulsifier and a conventional emulsifier is adopted instead of a traditional micromolecule emulsifier or fluorine-containing emulsifier, so that the performance is improved, and the cost expenditure is reduced; water is used as a medium, but not an organic solvent, so that the method is pollution-free and environment-friendly.
Description
Technical field
The invention belongs to the macromolecule synthesising technology field, particularly a kind of fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation.
Background technology
The esters of acrylic acid material is the nearly 20 years novel high-grade materials that develop rapidly; Have plurality of advantages such as strong, the anti-ultraviolet of cohesiveness, film-forming properties is high, raw material is cheap and easy to get, synthesis technique is simple, obtained using widely in industries such as paint, coating, sizing agent, fabric finishing agents.What application was maximum at present is (methyl) acrylic acid esters co-polymer, vinyl acetate/(methyl) acrylic acid esters co-polymer and vinylbenzene/(methyl) acrylic acid esters co-polymer emulsion.
Along with the continuous development of society, the acrylic polymer consumption grows with each passing day, and its poor water resistance, low temperature become fragile, high temperature becomes glutinous and loses strong shortcoming and also be exposed in face of the people gradually.People require increasingly highly to material, and pure acrylic acid class material has been difficult to meet the demands, and for the broadened application scope, people often carry out modification to it, with the more excellent product of expectation obtained performance.Method comparatively commonly used is carried out fluorinated silicone modified exactly to it, method has two kinds usually: one of which, and adopt fluorinated acrylate monomer and acrylic ester monomer to carry out copolymerization, products therefrom recycle silicon alkane is coupling agent modified; Its two, be aided with fluorine-containing emulsifier earlier through copolyreaction formation performed polymer with fluorine-containing siloxanes (the Si-O-chain is a main chain, and fluoro-containing group is a side chain), obtain title product with propylene ester monomer copolymerization again.Can prepare the novel high polymer material that has combined propenoate, organosilicon and organic fluorine material advantage through these two kinds of methods, have a wide range of applications.But these two kinds of methods but exist following deficiency: can use organic solvent more or less in (1) reaction process, depart from very far away with current environmental protection, green new industrialization development course; (2) characteristic of fluorochemical monomer water and oil repellant causes it in polymerization process, to be difficult for being disperseed, and polymerization stability is poor, and raw material availability is low, and production cost is higher; (3) for fluorochemical monomer is fully disperseed; Often must add the great amount of conventional emulsifying agent or use extraordinary fluorine-containing emulsifier; So; The performance of emulsion can cause certain defective because of the existence of small-molecular emulsifier, uses emulsifying agent can cause the pollution of environment on the other hand in a large number, and the use of fluorine-containing emulsifier simultaneously can cause that also cost rises.
A kind of fluorine-containing cation type emulsion and preparation method thereof is disclosed in the CN 101070356A one Chinese patent application document; This method utilizes a kind of amphipathic fluoride block copolymer to be applied in the mini-emulsion polymerization as reactive emulsifier; When reducing manufacturing cost, obtained stable fluorine-containing cation type emulsion.
A kind of preparation method who contains fluorine-containing latex under the carboxy fluorocarbon furfactant composition action is disclosed in the CN 100999556A one Chinese patent application document; This method utilization contains the carboxyl fluorocarbon polymer and combines to form a kind of carboxy fluorocarbon furfactant composition that contains with an amount of cats product through electrostatic interaction; Under the effect of this mixture, polymerisable monomer through letex polymerization get final product the target emulsion.In the method, the use of fluorochemical surfactant has strengthened its production cost, and remaining cationic emulsifier also is disadvantageous to environmental protection in the system simultaneously.
A kind of preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion is disclosed in the CN 101348595A one Chinese patent application document; This method has been utilized the method for core-shell emulsion polymerization, utilizes an organosilane monomer, acrylate containing fluorine monomer, acrylic monomer and self-cross linking monomer under the effect of fluorine-containing emulsifier, to obtain the target emulsion.This method technology is simple, good emulsion stability, but owing to used fluorochemical surfactant and contained acrylic ester monomer, exist the cost problem equally.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation is provided, when being intended to improve stability of emulsion, reduce the production cost of emulsion.
For solving the problems of the technologies described above, realize above-mentioned technique effect, the present invention has adopted following technical scheme:
With the fluorine silicon acrylate copolymer emulsion and the method for reactive emulsifier preparation, the raw material compositing range is:
Acrylic ester monomer 18wt%～35wt%;
Conventional emulsifier 0.1 wt%～0.5 wt%;
Reactive emulsifier 0.4 wt%～5 wt%;
Initiator 0.1 wt%～1 wt%;
Silane coupling agent 0.3 wt%～3 wt%;
An organosilane monomer 0.1 wt%～10 wt%;
Organic fluorinated silicone monomer 0.1 wt%～10 wt%;
Cyclosiloxane open loop promotor 0.1 wt%～0.8 wt%;
Silane hydrolyzate suppressor factor 0.01 wt%～1 wt%;
All the other are deionized water;
Prepare the method for fluorine silicon acrylate copolymer emulsion with reactive emulsifier, may further comprise the steps:
Step (1) adds quantitative deionized water with other components such as required monomer, conventional emulsifier, reactive emulsifier and pH buffer reagents, preparatory emulsification 0.1～0.5h on constant temperature blender with magnetic force;
Step (2) places then under the high speed shear dispersion machine and stirs 5～25min with 3000～5000rpm speed;
Step (3) get dispersion liquid and initiator solution then respectively each 1/5～1/3 add in four-hole bottle, 50 ℃ down with nitrogen replacement reaction flask air three times, feeding nitrogen protection, and slowly be warming up to 75～80 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is in 1～2h;
Step (5) is warming up to 80～85 ℃ after dripping and finishing, and insulation reaction 1～8h naturally cools to room temperature, and using ammoniacal liquor to be adjusted to ph is about 8, promptly gets copolymer emulsion after the filtration.
Further, said acrylic ester monomer is one or more combinations of methyl acrylate, TEB 3K, Bing Xisuandingzhi, NSC 20956.
Further, said conventional emulsifier is anionic emulsifier, nonionic emulsifier or its combination; Can be alkyl-sulphate, AS etc. as said anionic emulsifier, like sodium lauryl sulphate, X 2073 etc.; Can be polyoxyethylene nonylphenol as said nonionic emulsifier, like TX-10, TX-7, or be TX10, like OP-10, OP-9 etc.
Further, said reactive emulsifier is the one or more combination in styrene type, allyl group (allyloxy) type, (methyl) acrylic type, acid/acrylic amide type, the maleic anhydride type.
Further, said initiator is a kind of in ammonium persulphate, Potassium Persulphate, the Sodium Persulfate.
Further, said silane coupling agent is the one or more combination in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, the γ-methacryloxypropyl three isopropoxy silane.
Further, said an organosilane monomer is the one or more combination in octamethylcyclotetrasiloxane, vinyl cyclotetrasiloxane, the octamethylcyclotetrasiloxane linear body.
Further, said organic fluorinated silicone monomer is 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane.
Further, said cyclosiloxane open loop promotor is the one or more combination in quaternary ammonium hydroxide, alkali metal hydroxide, the chain alkyl Phenylsulfonic acid.
Further, said silane hydrolyzate suppressor factor is the one or more combination in terepthaloyl moietie, the Ucar 35.
Beneficial effect of the present invention is:
1, the present invention adopts reactive emulsifier and the composite technology of conventional emulsifier to carry out polymerization, and when obtaining the stabilization of polymer emulsion, the electrical property of emulsion and mechanical property also are able to promote; On the other hand, the synergy of two kinds of dissimilar emulsifying agents has reduced both usage quantity alone, has reduced production cost obtaining under the prerequisite of better performance;
2, the present invention utilizes octamethylcyclotetrasiloxane, ring trifluoropropyl siloxane to carry out copolymerization for functional monomer and propenoate, and raw material is all widely-used in industry, thereby the preparation method has very high industrial application value.This emulsion is when filming; The segment of fluorine silicon is because its special property; Can be spontaneous in film process move to the surface that film contacts with air, the film surface of formation contains the fluorine element silicon, has to refuse water preferably, refuse oily characteristic; This compares with the latex film that utilizes other fluorine silicon monomer to make, and has similar effects;
3, in reaction process not with an organic solvent or medium, environmental protection, production technique is simple simultaneously, mild condition is easy to suitability for industrialized production.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is the fluorine silicon Yodo Sol GH 28 of embodiment of the invention preparation and the ir spectra comparison diagram of pure acrylic acid ester copolymer;
Fig. 2 is the water contact angle comparison diagram through the fluorine silicon acrylate copolymer emulsion of the embodiment of the invention preparation silk fabrics of handling and the silk fabrics of handling through pure-acrylic emulsion.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is described in further detail.
Embodiment one:
Prepare the method for fluorine silicon acrylate copolymer emulsion with reactive emulsifier, may further comprise the steps:
Step (1) adds reactive emulsifier 2-acrylamido-2-methyl propane sulfonic acid of 0.8wt%, the conventional emulsifier polyoxyethylene octylphenol ether of 0.5wt%, the Witco 1298 Soft Acid of 0.7wt%, the terepthaloyl moietie of 0.7wt% and the deionized water of 50wt% in beaker; Use massfraction be 5 wt% sodium bicarbonate aqueous solutions to regulate mixing solutions pH be 8, under 25 ℃, the stir speed (S.S.) of 100rpm with above-mentioned solution stirring 5min; Treat to add after emulsifying agent is uniformly dispersed the mix monomer (mix monomer accounts for 28 wt% of system total mass, and four kinds of monomeric mass ratioes are 17 ︰, 10 ︰, 8 ︰ 1) of TEB 3K, Bing Xisuandingzhi, ring trifluoro propyl silane and vinyltriethoxysilane;
The above-mentioned then mixing liquid of step (2) behind the rotating speed stirring 0.5h with 500rpm, changes it over to high speed shear dispersion machine under 25 ℃, get homodisperse liquid behind the speed stirring 20min with 4000rpm;
Step (3) is got 1/3 of dispersion liquid then and is added in the four-hole bottle, and adds the ammonium persulfate aqueous solution of 0.2wt%, and 50 ℃ down with nitrogen replacement reaction flask air three times, the feeding nitrogen protection, and slowly be warming up to 75 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is about 2h;
Step (5) is warming up to 80 ℃ after dripping and finishing, and insulation reaction 4h naturally cools to room temperature, and using ammoniacal liquor to regulate ph is 7～8, promptly gets copolymer emulsion after the filtration.
Embodiment two:
Step (1) adds reactive emulsifier 2-acrylamido-2-methyl propane sulfonic acid of 1.0wt%, the conventional emulsifier polyoxyethylene octylphenol ether of 0.5wt%, the Witco 1298 Soft Acid of 0.7wt%, the terepthaloyl moietie of 0.7wt% and the deionized water of 50wt% in beaker; The use massfraction is that the sodium bicarbonate aqueous solution adjusting mixing solutions pH of 5 wt% is 7; Under 25 ℃, the stir speed (S.S.) of 100rpm with above-mentioned solution stirring 5min; Treat to add after emulsifying agent is uniformly dispersed the mix monomer (mix monomer accounts for the 30wt% of system total mass, and five kinds of monomeric mass ratioes are 17 ︰, 10 ︰, 3 ︰, 5 ︰ 1) of TEB 3K, Bing Xisuandingzhi, octamethylcyclotetrasiloxane, ring trifluoro propyl silane and vinyltriethoxysilane;
The above-mentioned then mixing liquid of step (2) behind the rotating speed stirring 0.5h with 500rpm, changes it over to high speed shear dispersion machine under 25 ℃, get homodisperse liquid behind the speed stirring 15min with 5000rpm;
Step (3) is got 1/3 of emulsion then and is added in the four-hole bottle, and adds the ammonium persulfate aqueous solution of 0.3wt%, and 50 ℃ down with nitrogen replacement reaction flask air three times, the feeding nitrogen protection, and slowly be warming up to 80 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is about 2h;
Step (5) is warming up to 85 ℃ after dripping and finishing, and insulation reaction 6h naturally cools to room temperature, and using ammoniacal liquor to regulate ph is 7～8, promptly gets copolymer emulsion after the filtration.
Embodiment three:
Step (1) adds reactive emulsifier 2-acrylamido-2-methyl propane sulfonic acid of 1.0wt%, conventional emulsifier polyoxyethylene octylphenol ether and sodium lauryl sulphate miscellany (both mass ratioes are 1 ︰ 1), the Witco 1298 Soft Acid of 0.8wt%, the terepthaloyl moietie of 0.7wt% and the deionized water of 51wt% of 0.4wt% in beaker; The use massfraction is that the sodium bicarbonate aqueous solution adjusting mixing solutions pH of 5 wt% is 8; Under 25 ℃, the stir speed (S.S.) of 100rpm with above-mentioned solution stirring 5min; Treat to add after emulsifying agent is uniformly dispersed the mix monomer (mix monomer accounts for 29 wt% of system total mass, and five kinds of monomeric mass ratioes are 34 ︰, 20 ︰, 10 ︰, 6 ︰ 3) of TEB 3K, Bing Xisuandingzhi, octamethylcyclotetrasiloxane, ring trifluoro propyl silane and vinyltriethoxysilane silane;
The above-mentioned mixing liquid of step (2) under 25 ℃, stir 0.5h with the rotating speed of 500rpm after, change it over to high speed shear dispersion machine, stir 20min with the speed of 4000rpm and get homodisperse liquid;
Step (3) is got 1/3 of dispersion liquid then and is added in the four-hole bottle, and adds the ammonium persulfate aqueous solution of 0.3wt%, and 50 ℃ down with nitrogen replacement reaction flask air three times, the feeding nitrogen protection, and slowly be warming up to 75 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is about 2h;
Step (5) is warming up to 80 ℃ after dripping and finishing, and insulation reaction 6h naturally cools to room temperature, and using ammoniacal liquor to regulate ph is 7～8, promptly gets copolymer emulsion after the filtration.
Embodiment four
Step (1) adds reactive emulsifier 2-acrylamido-2-methyl propane sulfonic acid, 0.5wt% conventional emulsifier polyoxyethylene octylphenol ether, the Witco 1298 Soft Acid of 0.8wt%, the terepthaloyl moietie of 0.7wt% and the deionized water of 52wt% of 1.1wt% in beaker; Using massfraction is that 5 wt% sodium bicarbonate aqueous solutions adjusting mixing solutions pH is 8; Under 25 ℃, the stir speed (S.S.) of 100rpm with above-mentioned solution stirring 5min; Treat to add after emulsifying agent is uniformly dispersed the mix monomer (mix monomer accounts for 29 wt% of system total mass, and five kinds of monomeric mass ratioes are 17 ︰, 10 ︰, 3 ︰, 5 ︰ 1) of TEB 3K, Bing Xisuandingzhi, octamethylcyclotetrasiloxane, ring trifluoro propyl silane and γ-methacryloxypropyl trimethoxy silane;
The above-mentioned mixing liquid of step (2) under 25 ℃, stir 0.5h with the rotating speed of 500rpm after, change it over to high speed shear dispersion machine, stir 15min with the speed of 5000rpm and get homodisperse liquid;
Step (3) is got 1/3 of dispersion liquid then and is added in the four-hole bottle, and adds the ammonium persulfate aqueous solution of 0.3wt%, and 50 ℃ down with nitrogen replacement reaction flask air three times, the feeding nitrogen protection, and slowly be warming up to 75 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is about 2h;
Step (5) is warming up to 80 ℃ after dripping and finishing, and insulation reaction 4h naturally cools to room temperature, and using ammoniacal liquor to be adjusted to ph is 7～8, promptly gets copolymer emulsion after the filtration.
Embodiment five:
Step (1) adds reactive emulsifier 2-acrylamido-2-methyl propane sulfonic acid, 0.4wt% conventional emulsifier polyoxyethylene octylphenol ether, 0.6wt% Witco 1298 Soft Acid, 0.6wt% terepthaloyl moietie and the 50wt% deionized water of 1.5wt% in beaker; The use massfraction is that the sodium bicarbonate aqueous solution adjusting mixing solutions pH of 5 wt% is 7; Under 25 ℃, the stir speed (S.S.) of 100rpm with above-mentioned solution stirring 5min; Treat to add after emulsifying agent is uniformly dispersed the mix monomer (mix monomer accounts for 29 wt% of system total mass, and five kinds of monomeric mass ratioes are 20 ︰, 10 ︰, 3 ︰, 5 ︰ 1) of TEB 3K, Bing Xisuandingzhi, octamethylcyclotetrasiloxane, ring trifluoro propyl silane and γ-methacryloxypropyl three isopropoxy silane;
The above-mentioned mixing liquid of step (2) under 25 ℃, stir 0.5h with the rotating speed of 500rpm after, change it over to high speed shear dispersion machine, stir 15min with the speed of 5000rpm and get homodisperse liquid;
Step (3) is got 1/3 of dispersion liquid and is added in the four-hole bottle, and adds the ammonium persulfate aqueous solution of 0.3wt%, and 50 ℃ down with nitrogen replacement reaction flask air three times, the feeding nitrogen protection, and slowly be warming up to 80 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is about 2h;
After step (5) dripped and finishes, insulation reaction 5h naturally cooled to room temperature, and using ammoniacal liquor to regulate ph is 7～8, promptly gets copolymer emulsion after the filtration.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. with the fluorine silicon acrylate copolymer emulsion and the method for reactive emulsifier preparation, it is characterized in that the raw material compositing range is:
Acrylic ester monomer 18wt%～35wt%;
Conventional emulsifier 0.1 wt%～0.5 wt%;
Reactive emulsifier 0.4 wt%～5 wt%;
Initiator 0.1 wt%～1 wt%;
Silane coupling agent 0.3 wt%～3 wt%;
An organosilane monomer 0.1 wt%～10 wt%;
Organic fluorinated silicone monomer 0.1 wt%～10 wt%;
Cyclosiloxane open loop promotor 0.1 wt%～0.8 wt%;
Silane hydrolyzate suppressor factor 0.01 wt%～1 wt%;
All the other are deionized water;
Prepare the method for fluorine silicon acrylate copolymer emulsion with reactive emulsifier, it is characterized in that, may further comprise the steps:
Step (1) adds quantitative deionized water with other components such as required monomer, conventional emulsifier, reactive emulsifier and pH buffer reagents, preparatory emulsification 0.1～0.5h on constant temperature blender with magnetic force;
Step (2) places then under the high speed shear dispersion machine and stirs 5～25min with 3000～5000rpm speed;
Step (3) get dispersion liquid and initiator solution then respectively each 1/5～1/3 add in four-hole bottle, 50 ℃ down with nitrogen replacement reaction flask air three times, feeding nitrogen protection, and slowly be warming up to 75～80 ℃;
Begin behind the reactant reaction 0.5h in the remaining dispersion liquid question response of step (4) bottle to drip, and regularly add initiator, the control dropping time is in 1～2h;
Step (5) is warming up to 80～85 ℃ after dripping and finishing, and insulation reaction 1～8h naturally cools to room temperature, and using ammoniacal liquor to be adjusted to ph is about 8, promptly gets copolymer emulsion after the filtration.
2. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said acrylic ester monomer is one or more combinations of methyl acrylate, TEB 3K, Bing Xisuandingzhi, NSC 20956.
3. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said conventional emulsifier is anionic emulsifier, nonionic emulsifier or its combination; Can be alkyl-sulphate, AS etc. as said anionic emulsifier, like sodium lauryl sulphate, X 2073 etc.; Can be polyoxyethylene nonylphenol as said nonionic emulsifier, like TX-10, TX-7, or be TX10, like OP-10, OP-9 etc.
4. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said reactive emulsifier is the one or more combination in styrene type, allyl group (allyloxy) type, (methyl) acrylic type, acid/acrylic amide type, the maleic anhydride type.
5. fluorine silicon acrylate copolymer emulsion and method with reactive emulsifier preparation according to claim 1 is characterized in that: said initiator is a kind of in ammonium persulphate, Potassium Persulphate, the Sodium Persulfate.
6. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said silane coupling agent is the one or more combination in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, the γ-methacryloxypropyl three isopropoxy silane.
7. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said an organosilane monomer is the one or more combination in octamethylcyclotetrasiloxane, vinyl cyclotetrasiloxane, the octamethylcyclotetrasiloxane linear body.
8. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said organic fluorinated silicone monomer is 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane.
9. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said cyclosiloxane open loop promotor is the one or more combination in quaternary ammonium hydroxide, alkali metal hydroxide, the chain alkyl Phenylsulfonic acid.
10. fluorine silicon acrylate copolymer emulsion and method with the reactive emulsifier preparation according to claim 1, it is characterized in that: said silane hydrolyzate suppressor factor is the one or more combination in terepthaloyl moietie, the Ucar 35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110434369XA CN102516448A (en) | 2011-12-22 | 2011-12-22 | Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110434369XA CN102516448A (en) | 2011-12-22 | 2011-12-22 | Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102516448A true CN102516448A (en) | 2012-06-27 |
Family
ID=46287554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110434369XA Pending CN102516448A (en) | 2011-12-22 | 2011-12-22 | Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516448A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242479A (en) * | 2013-05-22 | 2013-08-14 | 南通福伦利新材料有限公司 | Fluorosilicone acrylates copolymer emulsion as well as preparation method and application thereof |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
| CN103694416A (en) * | 2013-12-11 | 2014-04-02 | 宁波润禾化学工业有限公司 | Preparation method of environment-friendly type fabric deepening agent |
| CN104844771A (en) * | 2015-04-22 | 2015-08-19 | 山东源根石油化工有限公司 | Water-proof, oil-proof and alcohol-proof emulsion and preparation method thereof |
| CN105131174A (en) * | 2015-08-20 | 2015-12-09 | 广东德美精细化工股份有限公司 | Durable uvioresistant finishing agent applicable to both cotton and terylene and preparation method thereof |
| CN105647445A (en) * | 2015-06-18 | 2016-06-08 | 苏州德捷膜材料科技有限公司 | High temperature resistant green fluorescence pressure-sensitive adhesive and preparation method thereof |
| CN108727923A (en) * | 2018-05-25 | 2018-11-02 | 吕标 | A kind of aqueous steel structure flame-retardant and thermal-insulated self-cleaning coating and preparation method thereof |
| CN110330852A (en) * | 2019-07-15 | 2019-10-15 | 长沙秋点兵信息科技有限公司 | Preparation method of waterproof coating for ceramic tiles |
| CN110642999A (en) * | 2019-10-28 | 2020-01-03 | 浙江理工大学 | Preparation method and application of fluorosilicone modified acrylate emulsion |
| CN111379177A (en) * | 2020-03-26 | 2020-07-07 | 珠海华大浩宏化工有限公司 | Organic silicon darkening finishing agent and preparation method thereof |
| CN112280379A (en) * | 2020-11-18 | 2021-01-29 | 梁贻波 | High-temperature-resistant ink composition and preparation method thereof |
| CN112457144A (en) * | 2020-12-11 | 2021-03-09 | 湖北航天化学技术研究所 | HMX explosive microsphere containing cross-linked fluoropolymer coating layer and preparation method thereof |
| CN115894771A (en) * | 2022-03-18 | 2023-04-04 | 上海启梦胶粘制品有限公司 | Acrylic latex and preparation method thereof |
| CN116285587A (en) * | 2023-04-11 | 2023-06-23 | 中烯新材料(福建)股份有限公司 | Thermal insulation coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN101302277A (en) * | 2008-06-16 | 2008-11-12 | 宁波润禾化学工业有限公司 | Functional fabric waterproof stiffener and preparation technology thereof |
| CN102127186A (en) * | 2010-12-28 | 2011-07-20 | 苏州工业园区优诺塑业有限公司 | Method for preparing fluorine-containing silicon acrylate emulsion |
-
2011
- 2011-12-22 CN CN201110434369XA patent/CN102516448A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN101302277A (en) * | 2008-06-16 | 2008-11-12 | 宁波润禾化学工业有限公司 | Functional fabric waterproof stiffener and preparation technology thereof |
| CN102127186A (en) * | 2010-12-28 | 2011-07-20 | 苏州工业园区优诺塑业有限公司 | Method for preparing fluorine-containing silicon acrylate emulsion |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382236B (en) * | 2013-05-12 | 2016-03-30 | 北京化工大学 | Silicon-acralyte latex of a kind of high silicone content and preparation method thereof |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
| CN103242479B (en) * | 2013-05-22 | 2015-07-29 | 南通福伦利新材料有限公司 | A kind of fluorine Si acrylate copolymer emulsion, preparation method and application |
| CN103242479A (en) * | 2013-05-22 | 2013-08-14 | 南通福伦利新材料有限公司 | Fluorosilicone acrylates copolymer emulsion as well as preparation method and application thereof |
| CN103694416A (en) * | 2013-12-11 | 2014-04-02 | 宁波润禾化学工业有限公司 | Preparation method of environment-friendly type fabric deepening agent |
| CN104844771B (en) * | 2015-04-22 | 2018-01-16 | 山东源根化学技术研发有限公司 | A kind of anti-alcohol emulsion of waterproof and oilproof and preparation method thereof |
| CN104844771A (en) * | 2015-04-22 | 2015-08-19 | 山东源根石油化工有限公司 | Water-proof, oil-proof and alcohol-proof emulsion and preparation method thereof |
| CN105647445A (en) * | 2015-06-18 | 2016-06-08 | 苏州德捷膜材料科技有限公司 | High temperature resistant green fluorescence pressure-sensitive adhesive and preparation method thereof |
| CN105131174A (en) * | 2015-08-20 | 2015-12-09 | 广东德美精细化工股份有限公司 | Durable uvioresistant finishing agent applicable to both cotton and terylene and preparation method thereof |
| CN108727923A (en) * | 2018-05-25 | 2018-11-02 | 吕标 | A kind of aqueous steel structure flame-retardant and thermal-insulated self-cleaning coating and preparation method thereof |
| CN110330852A (en) * | 2019-07-15 | 2019-10-15 | 长沙秋点兵信息科技有限公司 | Preparation method of waterproof coating for ceramic tiles |
| CN110642999B (en) * | 2019-10-28 | 2022-06-03 | 浙江理工大学 | Preparation method and application of fluorosilicone modified acrylate emulsion |
| CN110642999A (en) * | 2019-10-28 | 2020-01-03 | 浙江理工大学 | Preparation method and application of fluorosilicone modified acrylate emulsion |
| CN111379177A (en) * | 2020-03-26 | 2020-07-07 | 珠海华大浩宏化工有限公司 | Organic silicon darkening finishing agent and preparation method thereof |
| CN112280379A (en) * | 2020-11-18 | 2021-01-29 | 梁贻波 | High-temperature-resistant ink composition and preparation method thereof |
| CN112457144A (en) * | 2020-12-11 | 2021-03-09 | 湖北航天化学技术研究所 | HMX explosive microsphere containing cross-linked fluoropolymer coating layer and preparation method thereof |
| CN112457144B (en) * | 2020-12-11 | 2021-11-05 | 湖北航天化学技术研究所 | HMX explosive microsphere containing cross-linked fluoropolymer coating layer and preparation method thereof |
| CN115894771A (en) * | 2022-03-18 | 2023-04-04 | 上海启梦胶粘制品有限公司 | Acrylic latex and preparation method thereof |
| CN116285587A (en) * | 2023-04-11 | 2023-06-23 | 中烯新材料(福建)股份有限公司 | Thermal insulation coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102516448A (en) | Fluorine-containing silicon acrylate copolymer emulsion prepared by using reactive emulsifier and method | |
| CN103992421B (en) | The preparation method of Pickering acrylate polymer emulsions | |
| CN101423735B (en) | Method for preparing environment-friendly type organosilicon modified acrylic ester binding agent | |
| CN102786644A (en) | Preparation method of acrylic resin finishing agent modified by nano silicon dioxide (SiO2)-coated multi-walled carbon nanotubes | |
| CN103382344B (en) | Fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof | |
| CN102225982B (en) | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent | |
| CN103289010B (en) | Method for preparing core-shell nano SiO2/fluorine-containing polyacrylate soap-free emulsion | |
| CN101921373B (en) | Acrylic modified epoxy resin emulsion and preparation method thereof | |
| CN102134296B (en) | Fluosilicic modification water-soluble acrylic resin dispersion and uses thereof | |
| CN106749878B (en) | A kind of preparation of quaternary ammonium salt cationic type aqueous fluorine-containing polyacrylate and lotion and the lotion | |
| CN103289021A (en) | Waterborne organic and inorganic fluorosiloxane modified acrylate polymer emulsion and preparation method and application thereof | |
| CN105273556A (en) | Preparation method of polyacrylate/nano silicon dioxide composite emulsion coating material | |
| CN105732885A (en) | Method for preparing indoor temperature self-crosslinking acrylate emulsion of core-shell structure | |
| CN101831230A (en) | Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier | |
| CN102731735A (en) | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method | |
| CN103382236B (en) | Silicon-acralyte latex of a kind of high silicone content and preparation method thereof | |
| CN103224765A (en) | Fluorine-silicon-modified acrylate adhesive, preparation method and application thereof | |
| CN107805442A (en) | Graphene modified water-soluble anticorrosive paint and preparation method thereof | |
| CN106988134A (en) | A kind of printing adhesive and preparation method thereof, print paste and clothes | |
| CN103073673B (en) | Epoxy-group-containing fluorosilicone modified acrylate emulsion and preparation method thereof | |
| CN104448117A (en) | Water-based organic/inorganic hybrid acrylate emulsion and preparation method thereof | |
| CN104479067A (en) | Amphoteric ionic antistatic agent for acrylonitrile butadiene styrene (ABS) and preparation method of antistatic agent | |
| CN108442141B (en) | Environment-friendly high-temperature foaming slurry special for printing and dyeing and preparation method thereof | |
| CN102796231A (en) | Method for preparing ultraviolet curable waterborne silicone miniemulsion | |
| CN105970628B (en) | A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120627 |