CN104098736A - Hybrid silicon-modified acrylate emulsion, and application and preparation method thereof - Google Patents
Hybrid silicon-modified acrylate emulsion, and application and preparation method thereof Download PDFInfo
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- CN104098736A CN104098736A CN201310117061.1A CN201310117061A CN104098736A CN 104098736 A CN104098736 A CN 104098736A CN 201310117061 A CN201310117061 A CN 201310117061A CN 104098736 A CN104098736 A CN 104098736A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 132
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 239000010703 silicon Substances 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004160 Ammonium persulphate Substances 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 238000004945 emulsification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000009396 hybridization Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000004646 arylidenes Chemical group 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 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
- 229920003987 resole Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 7
- 238000010189 synthetic method Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- -1 acrylic ester Chemical class 0.000 description 30
- 238000010792 warming Methods 0.000 description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 238000009413 insulation Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920006222 acrylic ester polymer Polymers 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000005304 joining Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- 239000004925 Acrylic resin Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a hybrid silicon-modified acrylate emulsion, and application and a preparation method thereof. The hybrid silicon- modified acrylate emulsion is characterized by being prepared from a multifunctional silsesquioxane material containing a carbon-carbon double bond, an acrylate monomer, an emulsifier, water and an initiator. The preparation method does not need a catalyst, no by-product is generated, the synthetic method is simple, the product purity is high, and the cost is low. The obtained hybrid silicon-modified acrylate hybrid emulsion is stable in performances, and has extremely good high/low-temperature resistance, weatherability, water resistance and other performances.
Description
Technical field
The present invention relates to chemical industry sizing agent technical field, particularly a kind of Aqueous Adhesives composition and method of making the same of hybrid silicon-containing modified acrylate emulsion.
Background technology
Letex polymerization has that system viscosity is low, fast, the environmental protection and separate the features such as effect of conducting heat, and its product has been widely used in fields such as coating, paint, tackiness agent, rubber and medicament slow release capsule carriers.Olefin(e) acid resin refers to the homopolymer, multipolymer of acrylate monomer and the multipolymer with other vinyl monomers.Acrylic ester polymer is saturated compound, not containing residual double bonds, there is good resistance to UV, resistance to acids and bases, oxidation-resistance, adhesivity, erosion resistance and weathering resistance, become the important kind in coating and adhesive field and be widely used in the industry-by-industries such as rubber, plastics, coating, tackiness agent, fabric finishing agent.
Acrylic ester polymer high-and low-temperature resistance poor-performing.Meanwhile, acrylic ester polymer is because containing polarity ester group in molecular chain, although have better adhesive power, its water tolerance is poor, easily turn white, thereby the over-all properties that affects product even can occur to decompose ester group under certain condition after film water suction.In addition, the acrylic ester polymer particularly easy high temperature of linear polymer is clamminess, and contamination resistance declines, and low temperature becomes fragile, toughness variation.Acrylate resin molecule mostly is linear structure, lacks cross-linking set, thereby heat impedance is poor.
Si-O bond energy in organosilicon polymer (450 kJ/mol) is much larger than C-C bond energy (345 kJ/mol) and C-O bond energy (351 kJ/mol), patent 200980132542.1 discloses a kind of polyfunctionality silsesquioxane of carbon-carbon double bonds, because its molecular structure feature has, good resistant of high or low temperature, weathering resistance, ventilation property, hydrophobicity and anti-stain characteristic are good and surface tension is low, protect the performances such as light, water-fast, anti-efflorescence and ultraviolet light, but its sticking power is poor, can not normal temperature self-drying, film-forming properties is poor, bad to adhesion.Utilize the organosilicon component modification acrylic ester emulsion that bond energy is higher, surface can be lower, can be in conjunction with the high-performance of the two, the complementation of making the most of the advantage, improves high-and low-temperature resistance and the water resistance of acrylic ester polymer, thereby further expands its range of application.
Patent application 201010550379.5 discloses a kind of synthetic method of organic silicon modified propenoic ester copolymer, it adopts semicontinuous dripping method to synthesize organosilicon seed emulsion, by semicontinuous dripping method, use acrylic ester monomer graft copolymerization, synthesized the organosilicon-modified acrylate graft copolymer of high silicone content.Patent 201010186222.9 discloses a kind of organosilicon (methyl) acrylate ABA block polymer and preparation method thereof and application; it adopts atom transfer radical polymerization synthetic; by bromine or chlorine, polysiloxane or dimethyl siloxane and polysiloxane are carried out to end-blocking; bathe freezingly by cryosel, under nitrogen protection, catalyzed reaction obtains organic silicon acrylic ester ABA block polymer.The organosilicons such as siloxanes, polysiloxane and silane coupling agent contain siloxane structure, and siloxane structure is easy to hydrolysis and affects the package stability of emulsion.Above-mentioned document adopts these organosilicons to carry out modification to acrylate, and owing to containing siloxane structure in these organosilicons, the acrylate hybrid stability of emulsion of preparing is poor, affects the practical application of acrylate hybrid emulsion.
Although both at home and abroad researcher is to organic silicon acrylic ester emulsion system contrast deep research and discussion, but the polymer-modified stability of emulsion obtaining is still not good enough, easily separate, coacervation, its reason is mainly manifested in: the emulsion that is difficult to obtain polymerization, stable storing when 1. organosilicon addition is larger; 2. due to hydrolysis, the polycondensation of siloxanes, crosslinked gel and the emulsion viscosity of causing too early increases; 3. can impel the hydrolysis containing unsaturated double-bond silicon monomer in order to improve the appropriate acrylic acid or the like small molecules that the mechanical stability of emulsion adds, and in emulsion polymerization process, have the tendency of further autohemagglutination, cause the package stability variation of emulsion; 4. after polymerization completes, the low molecule of emulsifying agent still exists with unbound state, they adsorb, contain, are scattered in the surperficial or inner of emulsion polymer micelle, unstable to light, heat, oxygen, understand and affect the resistance to soiling of film, water tolerance, weathering resistance etc., thereby the water-resistant coating preparing, abrasion resistance and weathering resistance are not high.
Summary of the invention
Object of the present invention is exactly the deficiency in order to solve prior art and a kind of stable performance of providing, has the hybrid silicon-containing modified acrylate emulsion of the performances such as good resistant of high or low temperature, weathering resistance and water tolerance.
Another object of the present invention is to provide a kind of without catalyzer, and no coupling product produces, and synthetic method is simple, and product purity is high, the preparation method of the hybrid silicon-containing modified acrylate emulsion that cost is low.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of hybrid silicon-containing modified acrylate emulsion, it is characterized in that, it is to be prepared from by polyfunctionality silsesquioxane material, acrylate monomer, emulsifying agent, water and the initiator of carbon-carbon double bonds.
As further illustrating of such scheme, the polyfunctionality silsesquioxane material of described carbon-carbon double bonds, its skeleton symbol is:
R
n1R＇
n2[SiO
1.5]
8
In its structural formula, R, R ＇ are substituted radical, the functional group that R is carbon-carbon double bonds, and R ＇ is H, n1=1 ~ 8, n2=0 ~ 7.
Described R substituting group comprises the functional group of the carbon-carbon double bonds of alkyl, thiazolinyl, aryl, arylidene, acrylate-based, methacrylic ester.
Described acrylate monomer, is made up of soft monomer and hard monomer, and soft monomer comprises more than one in n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, n octyl methacrylate, Isooctyl acrylate monomer, Propylene glycol monoacrylate; Hard monomer comprises more than one in methyl methacrylate, vinylbenzene, vinylformic acid, methacrylic acid.
Described emulsifying agent is one or more in alkyl phenolic group Soxylat A 25-7, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, and its consumption is the 2.0-3.5% of acrylate monomer gross weight.
Described initiator is one or more in ammonium persulphate, Potassium Persulphate, S-WAT, and its consumption is the 0.7%-1.6% of acrylate monomer gross weight.
The consumption of described water is the 80%-100% of acrylate monomer gross weight.
A preparation method for hybrid silicon-containing modified acrylate emulsion, is characterized in that, it comprises the steps:
A, a polymerization:
By weight the polyfunctionality silsesquioxane of 90-99 part acrylate monomer A, 1-10 part carbon-carbon double bonds, 2-3.5 part emulsifying agent and 80-100 part water are mixed, pre-emulsification 10-30min, obtains pre-emulsion while stirring; The pre-emulsion of getting 1/3-1/10 weight, is heated to 60-70 DEG C, adds 0.3-0.8 part initiator A, in 70-80 DEG C of reaction 20-50min, obtains seed emulsion; Remaining pre-emulsion is added dropwise in 80-90 DEG C of seed emulsion, adds 0.3-0.8 part initiator B, 80-90 DEG C of reaction 3-4 hour, obtains polymerized emulsion one time;
B, after polymerization:
By 40-50 part acrylate monomer B, 1-2 part emulsifying agent and 40-50 part water pre-emulsification 10-30min at normal temperatures, obtain pre-emulsion by weight; Monomer emulsion is added in 80-90 DEG C of polymerized emulsion, add 0.1-0.4 part initiator C, carry out secondary letex polymerization, 90-95 DEG C is continued reaction 1-3 hour, cooling, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
The weight of described initiator A is preferably the 0.3%-0.8% of monomer A gross weight; The weight of initiator B is preferably the 0.3%-0.8% of monomer A gross weight; The weight of initiator C is preferably the 0.1%-0.4% of monomers B gross weight.
An Aqueous Adhesives composition for hybrid silicon-containing modified acrylate emulsion, is characterized in that, the hybrid silicon modification acrylate hybridisation emulsion synthesizing is mixed and made by certain mass ratio with other emulsions; Other emulsions here comprise at least one in vinyl acetate emulsion, neoprene emulsion, polyaminoester emulsion, epoxy resin latex, resol emulsion, organic silicon emulsion and rosin milk; In described sizing agent composition, the ratio of acrylate hybrid emulsion is 50%-99%.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
1, the present invention adopts seed emulsion polymerization, taking acrylate monomer as raw material, reacting of polyfunctionality silsesquioxane by acrylate monomer and carbon-carbon double bonds, silsesquioxane group is combined with the form of covalent linkage with acrylic ester polymer, further form the emulsion particle of nucleocapsid structure with acrylic ester monomer polymerization, the good stability of emulsion, and produce without condensation product, improve high-and low-temperature resistance and the water tolerance performance of acrylic ester polymer, further expanded the range of application of acrylic ester polymer.
2, the synthetic method of hybrid silicon modification acrylate provided by the invention, without catalyzer, no coupling product produces, and synthetic method is simple, and product purity is high, and cost is low; The stable performance of the hybrid silicon modification acrylate hybridisation emulsion obtaining, has the performances such as good resistant of high or low temperature, weathering resistance and water tolerance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
50g methyl allyl acyloxypropyl trimethoxysilane, 12g water, 100ml ethanol and 1g Tetramethylammonium hydroxide five hydrates are added in there-necked flask, 50 DEG C of magnetic agitation 48 h, vacuum rotary steam is removed alcoholic solvent and is obtained hydrolysate at 50 DEG C; Hydrolysate is dissolved in 100ml toluene,, filters until neutrality adds five water magnesium sulfates to dewater with saturated aqueous common salt solution washing toluene solution, 65 DEG C are reclaimed toluene, obtain prestox methyl acrylate base silsesquioxane.
Embodiment 2
A polymerization, 1.5 parts of alkylphenol polyoxyethylene (OP-10) are joined in three mouthfuls of round-bottomed flasks with 2 parts of sodium lauryl sulphate, add water 100 parts, mix, add 65 parts of n-butyl acrylates, 13 parts of methyl methacrylates, 12 parts of vinylbenzene, 5 parts of prestox methyl acrylate base silsesquioxanes, stirring velocity 1000r/min, pre-emulsification 30min; Get 0.5 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/6 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 70 DEG C, adds ammonium persulphate, is warming up to 75 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip residue pre-emulsions in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.5 part of ammonium persulphate, 90 DEG C of insulation reaction 2 hours;
After polymerization, joins 0.5 part of alkylphenol polyoxyethylene (OP-10) in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, adds water 50 parts, mix, add 20 parts of n-butyl acrylates, 13 parts of methyl methacrylates, 12 parts of vinylbenzene, stirring velocity 1000r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.4 part of ammonium persulphate; Be warming up to 95 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 3
A polymerization, 1 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 1 part of sodium lauryl sulphate, add water 80 parts, mix, add 30 parts of n-butyl acrylates, 20 parts of Isooctyl acrylate monomers, 40 parts of vinylbenzene, 10 parts of prestox methyl acrylate base silsesquioxanes, stirring velocity 500r/min, pre-emulsification 30min; Get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/10 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 70 DEG C, adds ammonium persulphate, is warming up to 80 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip and remain pre-emulsion in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.3 part of ammonium persulphate, insulation reaction 1 hour;
After polymerization, joins 0.5 part of alkylphenol polyoxyethylene (OP-10) in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, adds water 40 parts, mix, add 13 parts of n-butyl acrylates, 11 parts of Isooctyl acrylate monomers, 16 parts of vinylbenzene, stirring velocity 500r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.1 part of ammonium persulphate; Be warming up to 85 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 4
A polymerization, 1 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 1 part of sodium lauryl sulphate, add water 80 parts, mix, add 30 parts of n-butyl acrylates, 20 parts of Isooctyl acrylate monomers, 15 parts of methyl methacrylates, 25 parts of vinylbenzene, 10 parts of prestox methyl acrylate base silsesquioxanes, stirring velocity 500r/min, pre-emulsification 30min; Get 0.3 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/10 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 70 DEG C, adds ammonium persulphate, is warming up to 80 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip and remain pre-emulsion in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.3 part of ammonium persulphate, insulation reaction 1 hour;
After polymerization, 0.5 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, add water 40 parts, mix, add 13 parts of n-butyl acrylates, 11 parts of Isooctyl acrylate monomers, 9 parts of methyl methacrylates, 7 parts of vinylbenzene, stirring velocity 500r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.1 part of ammonium persulphate; Be warming up to 85 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 5
A polymerization, 1.5 parts of alkylphenol polyoxyethylene (OP-10) are joined in three mouthfuls of round-bottomed flasks with 2 parts of sodium lauryl sulphate, add water 80 parts, mix, add 45 parts of n-butyl acrylates, 25 parts of Isooctyl acrylate monomers, 5 parts of methyl methacrylates, 15 parts of vinylbenzene, 10 parts of prestox methyl acrylate base silsesquioxanes, stirring velocity 500r/min, pre-emulsification 10min; Get 0.8 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/3 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 60 DEG C, adds ammonium persulphate, is warming up to 70 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip and remain pre-emulsion in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.8 part of ammonium persulphate, insulation reaction 1 hour;
After polymerization, 0.5 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, add water 50 parts, mix, add 12 parts of n-butyl acrylates, 8 parts of Isooctyl acrylate monomers, 13 parts of methyl methacrylates, 17 parts of vinylbenzene, stirring velocity 1000r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.1 part of ammonium persulphate; Be warming up to 85 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 6
A polymerization, 1.5 parts of alkylphenol polyoxyethylene (OP-10) are joined in three mouthfuls of round-bottomed flasks with 2 parts of sodium lauryl sulphate, add water 100 parts, mix, add 45 parts of n-butyl acrylates, 26 parts of Isooctyl acrylate monomers, 13 parts of methyl methacrylates, 15 parts of vinylbenzene, 1 part of prestox methyl acrylate base silsesquioxane, stirring velocity 1000r/min, pre-emulsification 30min; Get 0.8 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/6 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 70 DEG C, adds ammonium persulphate, is warming up to 80 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip residue pre-emulsions in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.8 part of ammonium persulphate, 90 DEG C of insulation reaction 1 hour;
After polymerization, 0.5 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, add water 50 parts, mix, add 12 parts of n-butyl acrylates, 8 parts of Isooctyl acrylate monomers, 13 parts of methyl methacrylates, 17 parts of vinylbenzene, stirring velocity 1000r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.1 part of ammonium persulphate; Be warming up to 95 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 7
A polymerization, 1.5 parts of alkylphenol polyoxyethylene (OP-10) are joined in three mouthfuls of round-bottomed flasks with 2 parts of sodium lauryl sulphate, add water 100 parts, mix, add 45 parts of n-butyl acrylates, 13 parts of 20 parts of methyl methacrylates of Isooctyl acrylate monomer, 12 parts of vinylbenzene, 10 parts of prestox methyl acrylate base silsesquioxanes, stirring velocity 1000r/min, pre-emulsification 30min; Get 0.5 part of ammonium persulphate, be dissolved in 4 parts of water, the emulsion of getting 1/6 part of pre-emulsion total mass adds in three mouthfuls of round-bottomed flasks, is slowly warming up to 70 DEG C, adds ammonium persulphate, is warming up to 75 DEG C, initiated polymerization, and insulation 20min, obtains seed emulsion; Drip residue pre-emulsions in 80 DEG C, control rate of addition, in 2 hours, monomer dropping is complete, adds during this time 0.5 part of ammonium persulphate, 90 DEG C of insulation reaction 2 hours;
After polymerization, 0.5 part of alkylphenol polyoxyethylene (OP-10) is joined in three mouthfuls of round-bottomed flasks with 0.5 part of sodium lauryl sulphate, add water 50 parts, mix, add 12 parts of n-butyl acrylates, 13 parts of 8 parts of methyl methacrylates of Isooctyl acrylate monomer, 12 parts of vinylbenzene, stirring velocity 1000r/min, pre-emulsification 30min; Monomer emulsion is added in a polymerized emulsion, carry out secondary letex polymerization, the joining day is controlled at 2 hours, adds during this time 0.4 part of ammonium persulphate; Be warming up to 95 DEG C, be incubated cooling discharging after 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 8
Get 50 parts of acrylate hybrid emulsions that embodiment 4 is synthetic, 50 parts of ethylene-vinyl acetate emulsions, mix them, obtain the Aqueous Adhesives composition of acrylic ester emulsion.
Embodiment 9
Get 99 parts of acrylate hybrid emulsions that embodiment 5 is synthetic, 1 part of neoprene emulsion, mixes them, obtains the Aqueous Adhesives composition of acrylic ester emulsion.
Embodiment 10
Get 80 parts of acrylate hybrid emulsions that embodiment 6 is synthetic, 10 parts of neoprene emulsions, 10 parts of vinyl acetate emulsions mix them, obtain the Aqueous Adhesives composition of acrylic ester emulsion.
Embodiment 11
Get 80 parts of acrylate hybrid emulsions that embodiment 7 is synthetic, 20 parts of polyaminoester emulsions, 10 parts of vinyl acetate emulsions mix them, obtain the Aqueous Adhesives composition of acrylic ester emulsion.
Effect embodiment
The performance of hybrid silicon modification acrylate hybridisation emulsion prepared by embodiment 4-7 is tested, and test result is as follows:
。
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (10)
1. a hybrid silicon-containing modified acrylate emulsion, is characterized in that, it is to be prepared from by polyfunctionality silsesquioxane material, acrylate monomer, emulsifying agent, water and the initiator of carbon-carbon double bonds.
2. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 1, is characterized in that, the polyfunctionality silsesquioxane material of described carbon-carbon double bonds, and its skeleton symbol is:
R
n1R＇
n2[SiO
1.5]
8
In its structural formula, R, R ＇ are substituted radical, the functional group that R is carbon-carbon double bonds, and R ＇ is H, n1=1 ~ 8, n2=0 ~ 7.
3. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 2, is characterized in that, described R substituting group comprises the functional group of the carbon-carbon double bonds of alkyl, thiazolinyl, aryl, arylidene, acrylate-based, methacrylic ester.
4. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 1, it is characterized in that, described acrylate monomer, be made up of soft monomer and hard monomer, soft monomer comprises more than one in n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, n octyl methacrylate, Isooctyl acrylate monomer, Propylene glycol monoacrylate; Hard monomer comprises more than one in methyl methacrylate, vinylbenzene, vinylformic acid, methacrylic acid.
5. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 1, it is characterized in that, described emulsifying agent is one or more in alkyl phenolic group Soxylat A 25-7, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, and its consumption is the 2.0-3.5% of acrylate monomer gross weight.
6. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 1, is characterized in that, described initiator is one or more in ammonium persulphate, Potassium Persulphate, S-WAT, and its consumption is the 0.7%-1.6% of acrylate monomer gross weight.
7. a kind of hybrid silicon-containing modified acrylate emulsion according to claim 1, is characterized in that, the consumption of described water is the 80%-100% of acrylate monomer gross weight.
8. a preparation method for hybrid silicon-containing modified acrylate emulsion, is characterized in that, it comprises the steps:
A, a polymerization:
By weight the polyfunctionality silsesquioxane of 90-99 part acrylate monomer A, 1-10 part carbon-carbon double bonds, 2-3.5 part emulsifying agent and 80-100 part water are mixed, pre-emulsification 10-30min, obtains pre-emulsion while stirring; The pre-emulsion of getting 1/3-1/10 weight, is heated to 60-70 DEG C, adds 0.3-0.8 part initiator A, in 70-80 DEG C of reaction 20-50min, obtains seed emulsion; Remaining pre-emulsion is added dropwise in 80-90 DEG C of seed emulsion, adds 0.3-0.8 part initiator B, 80-90 DEG C of reaction 3-4 hour, obtains polymerized emulsion one time;
B, after polymerization:
By 40-50 part acrylate monomer B, 1-2 part emulsifying agent and 40-50 part water pre-emulsification 10-30min at normal temperatures, obtain pre-emulsion by weight; Monomer emulsion is added in 80-90 DEG C of polymerized emulsion, add 0.1-0.4 part initiator C, carry out secondary letex polymerization, 90-95 DEG C is continued reaction 1-3 hour, cooling, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
9. the preparation method of hybrid silicon-containing modified acrylate emulsion according to claim 8, is characterized in that, the weight of described initiator A is preferably the 0.3%-0.8% of monomer A gross weight; The weight of initiator B is preferably the 0.3%-0.8% of monomer A gross weight; The weight of initiator C is preferably the 0.1%-0.4% of monomers B gross weight.
10. an application for the hybrid silicon-containing modified acrylate emulsion as described in claim 1-9 any one, is characterized in that, it is the Aqueous Adhesives composition for making hybrid silicon-containing modified acrylate emulsion; The Aqueous Adhesives composition of hybrid silicon-containing modified acrylate emulsion is that the hybrid silicon modification acrylate hybridisation emulsion synthesizing is mixed and made by certain mass ratio with other emulsions; Other emulsions here comprise at least one in vinyl acetate emulsion, neoprene emulsion, polyaminoester emulsion, epoxy resin latex, resol emulsion, organic silicon emulsion and rosin milk; In described sizing agent composition, the ratio of acrylate hybrid emulsion is 50%-99%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408513A (en) * | 2011-10-13 | 2012-04-11 | 江苏博特新材料有限公司 | Preparation method of phosphate modified acrylate emulsion |
| CN102977253A (en) * | 2012-11-06 | 2013-03-20 | 中科院广州化学有限公司 | Silicone modified acrylate hybrid emulsion and preparation method and application thereof |
-
2013
- 2013-04-07 CN CN201310117061.1A patent/CN104098736B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408513A (en) * | 2011-10-13 | 2012-04-11 | 江苏博特新材料有限公司 | Preparation method of phosphate modified acrylate emulsion |
| CN102977253A (en) * | 2012-11-06 | 2013-03-20 | 中科院广州化学有限公司 | Silicone modified acrylate hybrid emulsion and preparation method and application thereof |
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