CN102351983B - Fluorine silicon acrylate copolymer, preparation process thereof and application thereof - Google Patents
Fluorine silicon acrylate copolymer, preparation process thereof and application thereof Download PDFInfo
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- CN102351983B CN102351983B CN 201110227445 CN201110227445A CN102351983B CN 102351983 B CN102351983 B CN 102351983B CN 201110227445 CN201110227445 CN 201110227445 CN 201110227445 A CN201110227445 A CN 201110227445A CN 102351983 B CN102351983 B CN 102351983B
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- -1 siloxanes Chemical class 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 229940043232 butyl acetate Drugs 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 3
- 229940065472 octyl acrylate Drugs 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005504 styryl group Chemical group 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000176 photostabilization Effects 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 229960002703 undecylenic acid Drugs 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a fluorine silicon acrylate copolymer, a preparation process thereof and an application thereof. The fluorine silicon acrylate copolymer is represented by formula 1 shown in the specification, and the preparation process of the copolymer is characterized in that: the fluorine silicon acrylate copolymer is prepared through carrying out a free radical quarternary random copolymerization method on a hard acrylate monomer, a soft acrylate monomer, a functional acrylate monomer containing hydroxyl, carboxyl or siloxane, and caged siloxane with a functional acrylic acid monomer containing fluorine and a functional monomer containing organosilicon in a solvent. The fluorine silicon acrylate copolymer which has the advantages of simple synthetic process, mild and easily controlled reaction condition, convenient industrialization, low surface energy and strong hydrophobicity after the film forming of the copolymer, and certain hardness and strength, can be directly mixed with a solvent and a curing agent to prepare a coating for use without adding inorganic fillers of a reinforcing agent and the like, and allows the prepared coating to have good ice and snow resistant performances.
Description
Technical field
The present invention relates to a kind of fluorine Si acrylate copolymer and its preparation method and application, belong to fluorine Si acrylate copolymer technical field.
Background technology
Acrylic acid esters co-polymer has good photostabilization, weathering resistance, ultraviolet resistance irradiation, erosion resistance, film forming properties with its acrylic ester coating of making is good, the water tolerance of its paint film, photostabilization, alkali resistance, ageing resistance and tint retention are comparatively outstanding, and good workability arranged, be that a class is used coating very widely, but have also that pollution resistance, weathering resistance are bad, physical strength and a shortcoming such as hardness is slightly poor.in recent years, people are studied the various modifications of acrylate copolymer, and someone passes through to have introduced fluoro-containing group or organosilicon radical in acrylic ester polymer, and the introducing of fluoro-containing group can reduce surface energy (all honest and just Bins of acrylate copolymer greatly, Wen Xiufang, Pi Pihui, Cai Zhiqi, Cheng Jiang, Yang Zhuoru, electroplate and cover with paint, lacquer, colour wash, etc. 2010,29 (8): 50-53), the introducing of organosilicon radical can give acrylate copolymer good low-temperature performance, snappiness, erosion resistance, with the common collaboration of fluoro-containing group, except improving the low-temperature performance weak point of acrylate copolymer, also have the advantage (Ni Yong such as good moistening perviousness and self-cleaning performance, the Zhao Yu rope, come state's bridge, Wu Jirong, organosilicon material, 2005, 19 (2): 14-16), fluoro-containing group or organosilicon radical form " shielding protection " effect to main chain and interior molecules, thereby make acrylic ester polymer after modification effectively improve the over-all properties of paint film, as good unreactiveness, weathering resistance, pollution resistance, hydrophobic and oil repellent etc., all obtained using more widely (Yang Hao at numerous areas, Zhang Xingjuan, Wang Xibo, Huang Ermei, Pi Pihui, Yang Zhuoru, electroplate and cover with paint, lacquer, colour wash, etc., 2010, 29 (1): 41-45).
As everyone knows, organosilicon and fluorine material are the bi-materials that in the nature all substances, known surface can be minimum, so the fluorine Si acrylate copolymer is also one of preferred material of preparation hydrophobic coating.The prepared hydrophobic coating of fluorine Si acrylate copolymer can be at Anti-ice-and-snow, antifouling, automatically cleaning and with aspects such as biological blood consistencies, potential application prospect is arranged.The POSS compound with regular structure, hollow dead front type or the type semienclosed siloxanes of a class organic inorganic hybridization, small-sized, diameter is about 1.5nm, molecular weight can pass through chemical bonding or physical blending and polymkeric substance and generate organic-inorganic hybrid material up to 1000, and POSS has in the polymer hybrid material of its formation to the characteristics of surface transport and self-assembly, POSS introduces the surfaceness that can increase co-polymer membrane in polymkeric substance, improves the hydrophobic performance of polymkeric substance.The disclosed one piece of patent of application is to adopt terpolymer to prepare fluorine-containing POSS acrylic copolymer resin recently, is applied in (cold generation is big, Hu Wen, Wu Ping, CN200910107167.7) on antifouling paint.
Intensity and the hardness of the fluorine Si acrylate copolymer of current preparation are not ideal enough, have limited the application of fluorine Si acrylate copolymer, the particularly application in the hydrophobic Anti-ice-and-snow coating of preparation, and not yet find relevant report.
Summary of the invention
The object of the present invention is to provide a kind of fluorine Si acrylate copolymer and its preparation method and application, this multipolymer has the surface can be low, and hydrophobicity is strong, and its preparation method is simple, for the preparation of the Anti-ice-and-snow hydrophobic coating.
The present invention realized by the following technical programs, and a kind of fluorine Si acrylate copolymer is characterized in that, the structural formula of this fluorine Si acrylate copolymer is shown in formula 1, the number-average molecular weight of multipolymer
For: 8000～30000, molecular weight distributing index
Be 1.5～2.8, heat decomposition temperature T when mass loss is 5%
d 5〉=400 ℃, after the multipolymer film forming to the contact angle of water greater than 110 °.
Formula 1
R
7For
In this structural unit, R is alkyl or fluorinated alkyl.
The preparation method of above-mentioned fluorine Si acrylate copolymer is characterized in that comprising following process:
press the quality of acrylate hard monomer, mass ratio with the acrylate soft monomer, mass ratio with the acrylate monomer that contains hydroxyl or carboxyl or functional polyorganosiloxane, mass ratio with the functional fluoropolymer Acrylic Acid Monomer, with the cage modle siloxanes mass ratio that contains organic functional silicon monomer be 1: (0.5～1.3): (0.06～0.2): (0.2～0.8): (0～0.13), and by the quality of above-mentioned total monomer and the mass ratio of initiator, with the mass ratio of solvent be 1: (0.005-0.03): (0.7-1.5), at first 1/3 initiator of consumption and the solvent of consumption 1/2 are added in reactor, at 30～80 ℃ of temperature, drip the acrylate hard monomer in reactor, the acrylate soft monomer, 1/4 the solvent mixture that contains 1/3 initiator of the function acrylate monomer of hydroxyl or carboxyl or siloxanes and consumption and consumption, after dropwising, after being warming up to 80～110 ℃ of polyase 13～6 hour, drip again the functional fluoropolymer acrylate monomer in the reactor or contain the cage modle siloxanes of organic functional silicon monomer and the solvent of remaining 1/3 initiator of consumption and consumption remaining 1/4 continues reaction 3～45 hours, reaction finishes, be cooled to the chamber discharging, obtain the fluorine Si acrylate copolymer.
Above-mentioned acrylate hard monomer, be selected from cyclohexyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate and isobornyl acrylate wherein one kind or two kinds, for the polymer super-hydrophobic coating provides certain hardness, and the motion of restriction side-chain radical.
Above-mentioned acrylate soft monomer is selected from wherein one or both of butyl acrylate, Octyl acrylate, stearyl methacrylate, lauryl methacrylate(LMA), for the polymer super-hydrophobic coating provides certain snappiness.
The acrylate monomer of the above-mentioned function that contains hydroxyl or carboxyl or siloxanes is selected from wherein one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, undecylenic acid, vinyl carbinol, vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane.
Above-mentioned functional fluoropolymer acrylate monomer, be selected from wherein one or both of vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters and vinylformic acid perfluoro alkyl ethyl, give polymkeric substance with low surface energy.
The above-mentioned cage modle siloxanes that contains organic functional silicon monomer, be selected from wherein a kind of of 4-methacryloxy butyl-seven isobutyl-POSS and 4-methacryloxy butyl-seven styryl POSS, the introducing one of POSS is to improve the coating hydrophobic performance, the 2nd, can change the coatingsurface pattern.
Above-mentioned initiator is selected from wherein one or both of Diisopropyl azodicarboxylate and the different benzoyl of peroxidation two.
Above-mentioned solvent is selected from wherein one or both of hexone, toluene, dimethylbenzene, butylacetate and pimelinketone.
Fluorine Si acrylate copolymer above-mentioned or the aforesaid method preparation is used, for the preparation of hydrophobic Anti-ice-and-snow coating and coating.
The invention has the advantages that: the one, adopt fluorine monomer or organosilane monomer to postpone the method that drips, be conducive to fluoro-containing group to surface transport, can improve the utilization ratio of coating fluorine monomer; Simple synthetic method, industrialization is convenient in the gentle easily control of reaction conditions.The 2nd, after this multipolymer film forming, have lower surface energy, hydrophobicity is strong; The 3rd, have certain hardness and intensity after this multipolymer film forming; Can need not to add the mineral filler such as toughener can be directly and solvent and solidifying agent be mixed with coating and use, prepared coating has good Anti-ice-and-snow performance.
Embodiment
Below by specific examples, the present invention is described, but the present invention is not only limited to these examples.
Embodiment 1
add 10g hexone and 0.05g Diisopropyl azodicarboxylate in reactor (250ml), logical nitrogen, be heated to temperature 60 C, drip two kinds of mixing solutionss to reactor again, wherein a kind of mixing solutions is by the 12g cyclohexyl methacrylate, the 9g Octyl acrylate, 2g hydroxyethyl methylacrylate and 15g hexone form, another kind of mixing solutions is comprised of 5g hexone and 0.05g Diisopropyl azodicarboxylate, reaction 3h, then slowly drip remaining 0.05g Diisopropyl azodicarboxylate and 3g methacrylic acid ten trifluoro monooctyl esters and 3g vinylformic acid trifluoro ethyl ester, 1g 4-methacryloxy butyl-seven styryl POSS and remaining 5g hexone, reaction 24h finishes, cooling, obtain translucent milkiness solution.
Adopt GPC-MwA type gel chromatograph, record the multipolymer number-average molecular weight
Be 16000, molecular weight distributing index
The contact angle that adopts JC2000D type contact angle measurement to record after the multipolymer film forming with water is 115 °.
Embodiment 2
Add 10g dimethylbenzene and 0.2g Diisopropyl azodicarboxylate at the 250mL reactor, logical nitrogen is heated to 80 ℃.Then drip the mixed solution that is formed by 12g cyclohexyl acrylate, 6g butyl acrylate, 0.72g vinyltriethoxysilane and 5g dimethylbenzene, drip simultaneously the solution that is formed by 5g dimethylbenzene and 0.2g Diisopropyl azodicarboxylate.After reaction 3h, then the 0.2g Diisopropyl azodicarboxylate and 2.4g dodecafluoroheptyl methacrylate and the 5g dimethylbenzene that drip.Continue to be down to room temperature after reaction 24h, obtain translucent milkiness solution.
Adopt GPC-MwA type gel chromatograph, the GPC method records the multipolymer number-average molecular weight
Molecular weight distributing index
The contact angle of filming with water is 110 °.
Embodiment 3
Add the 30g butylacetate in reactor (250ml), logical nitrogen is heated to 80 ℃.With dripping by 12g cyclohexyl methacrylate, 15.6g stearyl methacrylate, 2.4g undecylenic acid, reaching the solution that the 15g hexone forms, drip with another constant pressure funnel the solution that is formed by 15g butylacetate and 0.3g dibenzoyl peroxide simultaneously, be warming up to 110 ℃, react approximately 3h.Then slowly drip remaining 0.15g dibenzoyl peroxide and 6g vinylformic acid perfluoro alkyl ethyl, 15g butylacetate, reaction 24h finishes, and cooling obtains translucent milkiness solution.The mixture that is dissolved in 65g ethyl acetate and 25g toluene under above-mentioned 10g fluorine Si acrylate copolymer room temperature is mixed with solution, and ultra-sonic oscillation are coated on clean sheet glass dry 24h under room temperature after dissolving.
The GPC method records the multipolymer number-average molecular weight
Be 24000, molecular weight distributing index
Contact angle with water after employing JC2000D type contact angle measurement multipolymer film forming is 114 °.
Embodiment 4
Add the 8g pimelinketone in reactor (250ml), logical nitrogen is heated to 70 ℃.With dripping by 10g isobornyl acrylate, 10g lauryl methacrylate(LMA), 2g γ-methacryloxypropyl trimethoxy silane, reaching the solution that the 10g pimelinketone forms, drip with another constant pressure funnel the solution that is formed by 4g pimelinketone and 0.3g Diisopropyl azodicarboxylate simultaneously, react approximately 3h.Then slowly drip remaining 0.15g Diisopropyl azodicarboxylate and 2g Hexafluorobutyl mathacrylate, 3g trifluoroethyl methacrylate and remaining 10g pimelinketone, reaction 10h finishes, and cooling obtains translucent milkiness solution.The mixture that is dissolved in 65g ethyl acetate and 25g toluene under above-mentioned 10g fluorine Si acrylate copolymer room temperature is mixed with solution, and ultra-sonic oscillation are coated on clean sheet glass dry 24h under room temperature after dissolving.
The GPC method records the multipolymer number-average molecular weight
Be 30000, molecular weight distributing index
Contact angle with water after the multipolymer film forming is 112 °.
Embodiment 5
The toluene that adds 15g in reactor (250ml), logical nitrogen is heated to 90 ℃.With dripping by isobornyl methacrylate (10g), octadecyl acrylate (10g), vinyl carbinol (2g), reaching the solution that toluene (18g) forms, drip with another constant pressure funnel the solution that is formed by toluene (4g) and dibenzoyl peroxide (0.3g) simultaneously, reaction approximately 3 hours.Then slowly drip remaining dibenzoyl peroxide (0.15g) and Hexafluorobutyl mathacrylate (5g) and remaining toluene (10g) and 4-methacryloxy butyl-seven isobutyl-POSS (1g), reaction 45h finishes, cooling, obtain translucent milkiness solution, cool to 30 ℃, discharging is preserved.The mixture that is dissolved in 65g ethyl acetate and 25g toluene under above-mentioned 10g fluorine Si acrylate copolymer room temperature is mixed with solution, and ultra-sonic oscillation are coated on clean sheet glass dry 24h under room temperature after dissolving.
The GPC method records the multipolymer number-average molecular weight
Be 1.3 * 10
4, molecular weight distributing index
Contact angle with water after the multipolymer film forming is 116 °.
Claims (9)
1. the preparation method of a fluorine Si acrylate copolymer, the structural formula of described fluorine Si acrylate copolymer is shown in formula 1, the number-average molecular weight of multipolymer
For: 8000～30000, molecular weight distributing index
Be 1.5～2.8, heat decomposition temperature when mass loss is 5%, T
d 5〉=400 ℃, after the multipolymer film forming to the contact angle of water greater than 110 °,
In formula: R
1, R
2, R
3, R
4Be H or CH
3
R
5For
Or be
R
6For
Or be
Or be
Or be
R
fFor
R
7For
In this structural unit, R is alkyl or fluorinated alkyl,
It is characterized in that comprising following process:
press the quality of acrylate hard monomer, mass ratio with the acrylate soft monomer, mass ratio with the acrylate monomer that contains hydroxyl or carboxyl or functional polyorganosiloxane, mass ratio with the functional fluoropolymer Acrylic Acid Monomer, with the mass ratio of the cage modle siloxanes that contains organic functional silicon monomer be 1: (0.5～1.3): (0.06～0.2): (0.2～0.8): (0～0.13), and by the quality of above-mentioned total monomer and the mass ratio of initiator, with the mass ratio of solvent be 1: (0.005～0.03): (0.7～1.5), at first 1/3 initiator of consumption and the solvent of consumption 1/2 are added in reactor, at 30～80 ℃ of temperature, drip the acrylate hard monomer in reactor, the acrylate soft monomer, 1/4 the solvent mixture that contains 1/3 initiator of the function acrylate monomer of hydroxyl or carboxyl or siloxanes and consumption and consumption, after dropwising, after being warming up to 80～110 ℃ of polyase 13～6h, drip the functional fluoropolymer acrylate monomer or contain the cage modle siloxanes of organic functional silicon monomer and the solvent continuation reaction 3～45h of remaining 1/3 initiator of consumption and consumption remaining 1/4 in reactor again, reaction finishes, be cooled to the chamber discharging, obtain the fluorine Si acrylate copolymer.
2. press the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that, the acrylate hard monomer is selected from wherein one or both of cyclohexyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate and isobornyl acrylate.
3. by the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that the acrylate soft monomer is selected from wherein one or both of butyl acrylate, Octyl acrylate, stearyl methacrylate and lauryl methacrylate(LMA).
4. press the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that, the acrylate monomer that contains the function of hydroxyl or carboxyl or siloxanes is selected from wherein one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
5. press the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that, the functional fluoropolymer acrylate monomer is selected from wherein one or both of vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, methacrylic acid ten trifluoro monooctyl esters and vinylformic acid perfluoro alkyl ethyl.
6. press the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that, the cage modle siloxanes that contains organic functional silicon monomer is selected from wherein a kind of of 4-methacryloxy butyl-seven isobutyl-POSS and 4-methacryloxy butyl-seven styryl POSS.
7. by the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that initiator is selected from wherein one or both of Diisopropyl azodicarboxylate and the different benzoyl of peroxidation two.
8. by the preparation method of fluorine Si acrylate copolymer claimed in claim 1, it is characterized in that, solvent is selected from wherein one or both of hexone, toluene, dimethylbenzene, butylacetate and pimelinketone.
9. the fluorine Si acrylate copolymer by method preparation claimed in claim 1 is used, for the preparation of hydrophobic Anti-ice-and-snow coating and coating.
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| CN102127186B (en) * | 2010-12-28 | 2012-09-19 | 苏州工业园区优诺塑业有限公司 | Method for preparing fluorine-containing silicon acrylate emulsion |
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