CN104098736B - Hybrid silicon-containing modified acrylate emulsion and application thereof and preparation method - Google Patents
Hybrid silicon-containing modified acrylate emulsion and application thereof and preparation method Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 116
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000009396 hybridization Methods 0.000 claims abstract description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 58
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- -1 polyoxyethylene Polymers 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- 238000010792 warming 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 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 239000003999 initiator Substances 0.000 abstract description 9
- 239000003995 emulsifying agent Substances 0.000 abstract description 6
- 238000010189 synthetic method Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910020381 SiO1.5 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000006750 UV protection Effects 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
- 125000003118 aryl group Chemical group 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
- 239000011230 binding agent Substances 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
- 239000002775 capsule Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 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 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of hybrid silicon-containing modified acrylate emulsion and application thereof and preparation method, it is characterised in that it is to be prepared from by polyfunctionality silsesquioxane materials, acrylate monomer, emulsifying agent, water and the initiator of carbon-carbon double bonds.The present invention produces without catalyst, no coupling product, and synthetic method is simple, and product purity is high, low cost；The stable performance of obtained hybrid silicon modification acrylate hybridisation emulsion, has the performances such as good resistant of high or low temperature, weatherability and resistance to water.
Description
Technical field
The present invention relates to chemical industry adhesive technical field, particularly to the Aqueous Adhesives compositions and preparation method thereof of a kind of hybrid silicon-containing modified acrylate emulsion.
Background technology
Emulsion polymerization has that system viscosity is low, heat transfer is fast, environmental protection and separate the features such as effect, and its product has been widely used in fields such as coating, paint, binding agent, rubber and drug release capsules carriers.Olefin(e) acid resin refers to the homopolymer of acrylate monomer, copolymer and the copolymer with other vinyl monomers.Acrylate polymer is saturated compounds, without residual double bonds, there is excellent uv-resistance, resistance to acids and bases, non-oxidizability, adhesiveness, corrosion resistance and weatherability, it has also become important kind in coating and adhesive field is also widely used in the industry-by-industries such as rubber, plastics, coating, adhesive, fabric finishing agent.
Acrylate polymer high-and low-temperature resistance poor-performing.Meanwhile, acrylate polymer is because containing polar ester groups in strand, although have preferable adhesion, but its resistance to water is poor, easily turns white after film water suction, and ester group even can be decomposed thus be affected the combination property of product under certain condition.Additionally, the easy high temperature of acrylate polymer particularly linear polymer is tacky, stain resistance declines, and low temperature becomes fragile, degraded toughness.Acrylate molecule mostly is linear structure, lacks crosslinking points, thus heat resistance is poor.
In organosilicon polymer, Si-O bond energy (450kJ/mol) is much larger than C-C bond energy (345kJ/mol) and C-O bond energy (351kJ/mol), patent 200980132542.1 discloses the polyfunctionality silsesquioxane of a kind of carbon-carbon double bonds, have because of its molecular structure feature that good resistant of high or low temperature, weatherability, breathability, hydrophobicity and anti-stain characteristic are good and surface tension is low, protect the performances such as light, water-fast, anti-powdering and ultraviolet light, but its adhesive force is poor, can not normal temperature self-drying, film property is poor, bad to adhesion.Utilize the organosilicon composition modified acrylate emulsion that bond energy is higher, surface energy is relatively low, can be in conjunction with the superior function of the two, complementation of making the most of the advantage, improves high-and low-temperature resistance and the water resistance of acrylate polymer, thus expands its range of application further.
Patent application 201010550379.5 discloses the synthetic method of a kind of organic silicon modified propenoic ester copolymer, it uses semicontinuous dripping method to synthesize organosilicon seed emulsion, by semicontinuous dripping method, use acrylic ester monomer graft copolymerization, synthesize 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 and application; it uses atom transfer radical polymerization to synthesize; by bromine or chlorine, polysiloxanes or dimethyl siloxane are blocked with polysiloxanes; by cryosel bath freezing, catalytic reaction obtains organic silicon acrylic ester ABA block polymer under nitrogen protection.The organosilicons such as siloxanes, polysiloxanes and silane coupler contain siloxane structure, and siloxane structure is susceptible to hydrolysis and affects the bin stability of emulsion.Above-mentioned document uses these organosilicons to be modified acrylate, and owing to containing siloxane structure in these organosilicons, the acrylate hybrid stability of emulsion prepared is poor, affects the actual application of acrylate hybrid emulsion.
In-depth study and discussion although organic silicon acrylic ester emulsion system is contrasted by domestic and international researcher, but the modified polymer emulsion stability obtained is not the best enough, be susceptible to separate, coacervation, its reason is mainly manifested in: 1. organosilicon addition be difficult to time bigger to be polymerized, the emulsion of stable storing；2. due to hydrolysis, the polycondensation of siloxy group, crosslinking causes gel and emulsion viscosity to increase too early；3. the appropriate acrylic acid micromolecular added to improve the mechanical stability of emulsion can promote the hydrolysis containing unsaturated double-bond silicon monomer, and has the tendency of further autohemagglutination in emulsion polymerization process, causes the bin stability of emulsion to be deteriorated；4. after being polymerized, emulsifying agent low molecule still exists with free state, they adsorb, contain, are scattered in surface or the inside of emulsion polymer micelle, to light, heat, oxygen instability, the resistance to soiling of film, resistance to water, weatherability etc. can be affected, thus the water-resistant coating prepared, abrasion resistance and weatherability are the highest.
Summary of the invention
A kind of stable performance that the purpose of the present invention is contemplated to solve the deficiency of prior art and provides, has the hybrid silicon-containing modified acrylate emulsion of the performances such as good resistant of high or low temperature, weatherability and resistance to water.
It is a further object of the present invention to provide a kind of without catalyst, 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 of low cost.
The present invention is to use following technical solution to be attained in that a kind of hybrid silicon-containing modified acrylate emulsion, it is characterized in that, it is to be prepared from by polyfunctionality silsesquioxane materials, acrylate monomer, emulsifying agent, water and the initiator of carbon-carbon double bonds.
Further illustrating as such scheme, the polyfunctionality silsesquioxane materials of described carbon-carbon double bonds, its skeleton symbol is:
Rn1R ＇n2[SiO1.5]8
In its structural formula, R, R ＇ is substituted radical, and R is the functional group of carbon-carbon double bonds, and R ＇ is H, n1=1 ~ 8, n2=0 ~ 7.
Described R substituent includes the functional group of the carbon-carbon double bonds of alkyl, thiazolinyl, aryl, arlydene, acrylate-based, methacrylate.
Described acrylate monomer, is made up of soft monomer and hard monomer, and soft monomer includes more than one in n-butyl acrylate, Isobutyl 2-propenoate, n-octyl, n octyl methacrylate, Isooctyl acrylate monomer, Hydroxypropyl acrylate；Hard monomer includes more than one in methyl methacrylate, styrene, acrylic acid, methacrylic acid.
Described emulsifying agent is one or more in alkyl phenolic group polyoxyethylene ether, sodium lauryl sulphate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, and its consumption is the 2.0-3.5% of acrylate monomer gross weight.
Described initiator is one or more in Ammonium persulfate., potassium peroxydisulfate, sodium sulfite, 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.
The preparation method of a kind of hybrid silicon-containing modified acrylate emulsion, it is characterised in that it comprises the steps:
A, once 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 while stirring, obtain pre-emulsion；Take the pre-emulsion of 1/3-1/10 weight, be heated to 60-70 DEG C, add 0.3-0.8 part initiator A, react 20-50min in 70-80 DEG C, obtain seed emulsion；Being added dropwise in 80-90 DEG C of seed emulsion by remaining pre-emulsion, add 0.3-0.8 part initiator B, 80-90 DEG C is reacted 3-4 hour, obtains a polymerized emulsion；
B, after polymerization:
By weight 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；Monomer emulsions is added in 80-90 DEG C of polymerized emulsion, adding 0.1-0.4 part initiator C, carry out secondary emulsion polymerization, 90-95 DEG C is continued reaction 1-3 hour, cooling, obtains 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 monomer B gross weight.
The Aqueous Adhesives compositions of a kind of hybrid silicon-containing modified acrylate emulsion, it is characterised in that the hybrid silicon modification acrylate hybridisation emulsion synthesized is mixed to prepare by certain mass ratio with other emulsions；Here other emulsions include at least one in vinyl acetate emulsion, neoprene emulsion, polyaminoester emulsion, epoxy resin latex, Phenolic resin emulsion, organic silicon emulsion and rosin milk；In described Adhesive composition, the ratio of acrylate hybrid emulsion is 50%-99%.
The present invention uses above-mentioned technical solution can reach to provide the benefit that:
1, the present invention uses seed emulsion polymerization, with acrylate monomer as raw material, reaction by acrylate monomer Yu the polyfunctionality silsesquioxane of carbon-carbon double bonds, silsesquioxane group is made to be combined with the form of covalent bond with acrylate polymer, the emulsion particle forming nucleocapsid structure it is polymerized further with acrylic ester monomer, emulsion intercalation method is good, and produce without condensation product, improve high-and low-temperature resistance and the resistance to water performance of acrylate polymer, expand the range of application of acrylate polymer further.
2, the synthetic method of the hybrid silicon modification acrylate that the present invention provides, it is not necessary to catalyst, no coupling product produces, and synthetic method is simple, and product purity is high, low cost；The stable performance of obtained hybrid silicon modification acrylate hybridisation emulsion, has the performances such as good resistant of high or low temperature, weatherability and resistance to water.
Detailed description of the invention
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 hydrate being added in there-necked flask, 50 DEG C of magnetic agitation 48h, at 50 DEG C, vacuum rotary steam removing alcoholic solvent obtains hydrolyzate；Being dissolved in by hydrolyzate in 100ml toluene, with saturated aqueous common salt solution washing toluene solution until neutrality, add five water magnesium sulfates and remove water, filter, 65 DEG C are reclaimed toluene, obtain prestox acrylic acid methyl ester. base silsesquioxane.
Embodiment 2
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1.5 parts and sodium lauryl sulphate 2 parts are joined in three neck round bottom flask, add water 100 parts, mixing, adds n-butyl acrylate 65 parts, methyl methacrylate 13 parts, styrene 12 parts, prestox acrylic acid methyl ester. base silsesquioxane 5 parts, mixing speed 1000r/min, pre-emulsification 30min；Taking 0.5 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/6 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 75 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.5 part, 90 DEG C of insulation reaction 2 hours；
After polymerization, joins in three neck round bottom flask by alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part, adds water 50 parts, mixing, adds n-butyl acrylate 20 parts, methyl methacrylate 13 parts, styrene 12 parts, mixing speed 1000r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.4 part；It is warming up to 95 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 3
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1 part and sodium lauryl sulphate 1 part are joined in three neck round bottom flask, add water 80 parts, mixing, adds n-butyl acrylate 30 parts, Isooctyl acrylate monomer 20 parts, styrene 40 parts, prestox acrylic acid methyl ester. base silsesquioxane 10 parts, mixing speed 500r/min, pre-emulsification 30min；Taking 0.3 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/10 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 80 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.3 part, insulation reaction 1 hour；
After polymerization, joins in three neck round bottom flask by alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part, adds water 40 parts, mixing, adds n-butyl acrylate 13 parts, Isooctyl acrylate monomer 11 parts, styrene 16 parts, mixing speed 500r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.1 part；It is warming up to 85 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 4
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1 part and sodium lauryl sulphate 1 part are joined in three neck round bottom flask, add water 80 parts, mixing, add n-butyl acrylate 30 parts, Isooctyl acrylate monomer 20 parts, methyl methacrylate 15 parts, styrene 25 parts, prestox acrylic acid methyl ester. base silsesquioxane 10 parts, mixing speed 500r/min, pre-emulsification 30min；Taking 0.3 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/10 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 80 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.3 part, insulation reaction 1 hour；
After polymerization, alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part are joined in three neck round bottom flask, add water 40 parts, mixing, adds n-butyl acrylate 13 parts, Isooctyl acrylate monomer 11 parts, methyl methacrylate 9 parts, styrene 7 parts, mixing speed 500r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.1 part；It is warming up to 85 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 5
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1.5 parts and sodium lauryl sulphate 2 parts are joined in three neck round bottom flask, add water 80 parts, mixing, add n-butyl acrylate 45 parts, Isooctyl acrylate monomer 25 parts, methyl methacrylate 5 parts, styrene 15 parts, prestox acrylic acid methyl ester. base silsesquioxane 10 parts, mixing speed 500r/min, pre-emulsification 10min；Taking 0.8 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/3 part adds in three neck round bottom flask, is to slowly warm up to 60 DEG C, adds Ammonium persulfate., is warming up to 70 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.8 part, insulation reaction 1 hour；
After polymerization, alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part are joined in three neck round bottom flask, add water 50 parts, mixing, adds n-butyl acrylate 12 parts, Isooctyl acrylate monomer 8 parts, methyl methacrylate 13 parts, styrene 17 parts, mixing speed 1000r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.1 part；It is warming up to 85 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 6
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1.5 parts and sodium lauryl sulphate 2 parts are joined in three neck round bottom flask, add water 100 parts, mixing, add n-butyl acrylate 45 parts, Isooctyl acrylate monomer 26 parts, methyl methacrylate 13 parts, styrene 15 parts, prestox acrylic acid methyl ester. base silsesquioxane 1 part, mixing speed 1000r/min, pre-emulsification 30min；Taking 0.8 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/6 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 80 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.8 part, 90 DEG C of insulation reaction 1 hour；
After polymerization, alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part are joined in three neck round bottom flask, add water 50 parts, mixing, adds n-butyl acrylate 12 parts, Isooctyl acrylate monomer 8 parts, methyl methacrylate 13 parts, styrene 17 parts, mixing speed 1000r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.1 part；It is warming up to 95 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 7
Once it is polymerized, alkylphenol polyoxyethylene (OP-10) 1.5 parts and sodium lauryl sulphate 2 parts are joined in three neck round bottom flask, add water 100 parts, mixing, adds n-butyl acrylate 45 parts, 20 parts of methyl methacrylates of Isooctyl acrylate monomer 13 parts, styrene 12 parts, prestox acrylic acid methyl ester. base silsesquioxane 10 parts, mixing speed 1000r/min, pre-emulsification 30min；Taking 0.5 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/6 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 75 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.5 part, 90 DEG C of insulation reaction 2 hours；
After polymerization, alkylphenol polyoxyethylene (OP-10) 0.5 part and sodium lauryl sulphate 0.5 part are joined in three neck round bottom flask, add water 50 parts, mixing, add n-butyl acrylate 12 parts, 8 parts of methyl methacrylates of Isooctyl acrylate monomer 13 parts, styrene 12 parts, mixing speed 1000r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.4 part；It is warming up to 95 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds.
Embodiment 8
Take the acrylate hybrid emulsion of 50 parts of embodiment 4 synthesis, 50 parts of ethylene-vinyl acetate emulsions, by they mix homogeneously, obtain the Aqueous Adhesives compositions of acrylic acid ester emulsion.
Embodiment 9
Take the acrylate hybrid emulsion of 99 parts of embodiment 5 synthesis, 1 part of neoprene emulsion, by they mix homogeneously, obtain the Aqueous Adhesives compositions of acrylic acid ester emulsion.
Embodiment 10
Taking the acrylate hybrid emulsion of 80 parts of embodiment 6 synthesis, 10 parts of neoprene emulsions, 10 parts of vinyl acetate emulsions, by they mix homogeneously, obtain the Aqueous Adhesives compositions of acrylic acid ester emulsion.
Embodiment 11
Taking the acrylate hybrid emulsion of 80 parts of embodiment 7 synthesis, 20 parts of polyaminoester emulsions, 10 parts of vinyl acetate emulsions, by they mix homogeneously, obtain the Aqueous Adhesives compositions of acrylic acid ester emulsion.
Effect example
The performance of the hybrid silicon modification acrylate hybridisation emulsion preparing embodiment 4-7 is tested, and test result is as follows:
。
Above-described is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, it is also possible to make some deformation and improvement, these broadly fall into protection scope of the present invention.
Claims (2)
1. the preparation method of a hybrid silicon-containing modified acrylate emulsion, it is characterised in that it comprises the steps:
Once it is polymerized, alkylphenol polyoxyethylene 1 part and sodium lauryl sulphate 1 part are joined in three neck round bottom flask, add water 80 parts, mixing, add n-butyl acrylate 30 parts, Isooctyl acrylate monomer 20 parts, methyl methacrylate 15 parts, styrene 25 parts, prestox acrylic acid methyl ester. base silsesquioxane 10 parts, mixing speed 500r/min, pre-emulsification 30min；Taking 0.3 part of Ammonium persulfate., be dissolved in 4 parts of water, the emulsion taking pre-emulsion gross mass 1/10 part adds in three neck round bottom flask, is to slowly warm up to 70 DEG C, adds Ammonium persulfate., is warming up to 80 DEG C, causes polymerization, is incubated 20min, obtains seed emulsion；In 80 DEG C of dropping residue pre-emulsions, controlling rate of addition, in 2 hours, monomer dropping is complete, and period adds Ammonium persulfate. 0.3 part, insulation reaction 1 hour；
After polymerization, alkylphenol polyoxyethylene 0.5 part and sodium lauryl sulphate 0.5 part are joined in three neck round bottom flask, add water 40 parts, mixing, adds n-butyl acrylate 13 parts, Isooctyl acrylate monomer 11 parts, methyl methacrylate 9 parts, styrene 7 parts, mixing speed 500r/min, pre-emulsification 30min；Being added in a polymerized emulsion by monomer emulsions, carry out secondary emulsion polymerization, the joining day controls at 2 hours, and period adds Ammonium persulfate. 0.1 part；It is warming up to 85 DEG C, cooling discharging after being incubated 1 hour, obtain the polyfunctionality silsesquioxane modification acrylate hybridisation emulsion of nucleocapsid structure carbon-carbon double bonds, be hybrid silicon-containing modified acrylate emulsion.
2. the application of hybrid silicon-containing modified acrylate emulsion prepared by the preparation method of a hybrid silicon-containing modified acrylate emulsion as claimed in claim 1, it is characterized in that, described hybrid silicon-containing modified acrylate emulsion is the Aqueous Adhesives compositions for making hybrid silicon-containing modified acrylate emulsion；Take the acrylate hybrid emulsion of 50 parts of synthesis, 50 parts of ethylene-vinyl acetate emulsions, by they mix homogeneously, obtain the Aqueous Adhesives compositions of acrylic acid ester emulsion.
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| CN110790875B (en) * | 2019-11-26 | 2022-04-19 | 深圳市东信硅材料有限公司 | Organic silicon modified acrylic emulsion adhesive and preparation method thereof |
| CN111019281B (en) * | 2019-12-19 | 2021-12-10 | 上海贝塔建筑科技有限公司 | Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion |
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| CN115011274B (en) * | 2022-06-24 | 2023-07-18 | 浙江权威胶粘制品有限公司 | Modified acrylic ester high-temperature-resistant adhesive tape and preparation method thereof |
| CN116082912B (en) * | 2022-12-15 | 2023-12-19 | 北京东方雨虹防水技术股份有限公司 | Vapor-permeable waterproof coating |
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