CN116120558B - Solvent-free synthesis method of crosslinkable modified polysiloxane - Google Patents
Solvent-free synthesis method of crosslinkable modified polysiloxane Download PDFInfo
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- CN116120558B CN116120558B CN202310125444.7A CN202310125444A CN116120558B CN 116120558 B CN116120558 B CN 116120558B CN 202310125444 A CN202310125444 A CN 202310125444A CN 116120558 B CN116120558 B CN 116120558B
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- crosslinkable
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- -1 polysiloxane Polymers 0.000 title claims abstract description 87
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 81
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 14
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 9
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 150000003254 radicals Chemical group 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229940032330 sulfuric acid Drugs 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- BZCWFJMZVXHYQA-UHFFFAOYSA-N 3-dimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C(C)=C BZCWFJMZVXHYQA-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006561 solvent free reaction Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- MNYLCGIJDZPKLE-UHFFFAOYSA-N 2-methylbutan-2-yloxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)CC MNYLCGIJDZPKLE-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- HNVMCAHOYIOFAQ-UHFFFAOYSA-N 3-dimethoxysilylpropyl prop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C=C HNVMCAHOYIOFAQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000010146 3D printing Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- YUXUHPPKFLTFSF-UHFFFAOYSA-N piperazine silane Chemical compound [SiH4].N1CCNCC1 YUXUHPPKFLTFSF-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The application provides a solvent-free synthesis method of crosslinkable modified polysiloxane and a solid modified siloxane polymer. According to the application, through optimizing the synthesis method, the specific unit monomer under the condition of completely containing no organic solvent is adopted to copolymerize to obtain the liquid polysiloxane, and then the liquid polysiloxane is crosslinked and solidified to form the siloxane high polymer, a series of problems of organic solvent pollution, metal catalyst residues, precise control of polymer molecular weight, repeated production and the like in the synthesis process can be effectively solved, and the wide application requirements are met.
Description
Technical Field
The application relates to the field of organosilicon polymeric materials, in particular to a solvent-free synthesis method of cross-linkable modified polysiloxane and a solid modified siloxane polymer.
Background
The polysiloxane is polymerized from siloxane monomers. Because of the special molecular structure, the polysiloxane has excellent physical and chemical properties, such as excellent heat resistance, radiation resistance, high temperature resistance, oxidation resistance, high light transmittance, high air permeability and the like, and is widely applied to the fields of electrician electronics, buildings, daily necessities, cosmetics, textiles and the like.
In the synthesis of polysiloxanes, a large amount of organic solvents such as toluene, heptane, octane, cyclohexane, etc. are often used. The use of the solvents brings great pollution to the environment, seriously threatens the survival and health of human beings, and on the other hand, the existence of organic impurities can influence the application of polysiloxane in products, so that complex post-treatment and purification of reaction products are required, and the resource consumption is high. Today, where environmental protection is becoming more and more important, the development of solvent-free polysiloxane synthetic routes clearly has good market prospects.
The application uses a completely solvent-free reaction system by optimizing the synthesis method, avoids the generation of organic waste liquid and the introduction of organic impurities, and is very beneficial to environmental protection and cost reduction.
Disclosure of Invention
In a first aspect of the present application, there is provided a solvent-free synthesis method of a crosslinkable modified polysiloxane, the synthesis process not using an organic solvent, comprising the steps of:
premixing: uniformly mixing 100 parts by mass of siloxane oligomer, 1-20 parts by mass of crosslinkable silane coupling agent monomer, 0.1-5 parts by mass of acid catalyst and 1-10 parts by mass of reaction control agent;
the reaction: heating the premixed mixture to a reaction temperature for reacting for a certain time, and after the reaction is finished; distilling to remove low boiling point substances to obtain the crosslinkable modified polysiloxane.
Further, the siloxane oligomer is one or more of hydroxyl terminated siloxane oligomer and methoxy terminated siloxane oligomer.
Further, the siloxane oligomer is one or more of dihydroxyl end-capped methyl phenyl siloxane oligomer, dimethoxy end-capped methyl phenyl siloxane oligomer, dihydroxyl end-capped methyl siloxane oligomer and dimethoxy end-capped methyl siloxane.
Further, the crosslinkable silane coupling agent monomer is one or more of an aminosilane coupling agent monomer, a mercapto silane coupling agent monomer, an isocyanate silane coupling agent monomer, a piperazine silane coupling agent monomer, a vinyl silane coupling agent monomer, an epoxy silane coupling agent monomer, a methacryloxy silane coupling agent monomer and an acryloxy silane coupling agent monomer.
Further, the acid catalyst is one or more of sulfuric acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and fluorosulfonic acid.
Further, the acid catalyst is one or more of benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and fluorosulfonic acid.
Further, the reaction control agent is water and/or acetic acid.
Further, the reaction temperature is 40-80 ℃ and the reaction time is 1-10 h.
Further, the reaction temperature is 50-60 ℃ and the reaction time is 2-5 h.
Further, the vacuum of the distillation is below 10mbar.
In order to obtain the crosslinkable modified polysiloxane with higher purity, the product obtained by the method can be purified by adopting the technical means known in the art such as reduced pressure distillation, extraction, alkali substance neutralization and acid catalyst with lower vacuum degree. If necessary, a small amount of solvent such as ethanol, n-heptane, toluene, etc. may be used to improve the purification efficiency. The alkaline substance can be sodium carbonate, sodium bicarbonate, calcium carbonate, etc.
In a second aspect of the present application, there is provided a crosslinkable modified polysiloxane synthesized by the solvent-free method described above; the main chain is siloxane, and the side chain contains at least one crosslinkable functional group, and its structure can be shown in the following figure
Wherein,
R 1 is one or more of hydrogen, alkyl, alkoxy and aromatic groups;
R 2 is a crosslinkable functional group selected from one or more of vinyl, amino, acryloxy, methacryloxy, mercapto, epoxy, isocyanate, and piperazine;
R 3 is one or more of hydrogen, hydroxyl and methoxy;
n=a positive integer of 1 to 100,000, and m=a positive integer of 1 to 10,000.
Further, the content of the crosslinkable functional group is 0.1-20% of the total mass of the polysiloxane.
Further, the polysiloxane has a molecular weight mn=1000 to 100,000 and a viscosity of 500 to 50,000cps.
Further, the polysiloxane structure may be a chain, network, three-dimensional stereo structure.
In a third aspect of the present application, there is provided a solid modified silicone polymer obtained by crosslinking and curing the crosslinkable modified polysiloxane under the initiation of an initiator under the action of light and/or heat.
Further, the light acts as UV light irradiation.
Further, the thermal action is to heat the crosslinkable modified polysiloxane to a temperature of 40 ℃ to 80 ℃. The higher the temperature, the faster the crosslinking curing reaction speed.
Further, the initiator is a cationic initiator and is selected from at least one of sulfonium salts, aryldiazonium salts, diarylhalonium salts and triarylhalonium salts.
Further, the initiator is a radical initiator selected from at least one of 184 (CAS No. 947-19-3), ITX (CAS No. 5495-84-1 or 83846-86-0), 819 (CAS No. 162881-26-7), 1173 (CAS No. 7473-98-5), BDK (CAS No. 24650-42-8), BP (CAS No. 119-61-9), TPO (CAS No. 75980-60-8), 369 (CAS No. 119313-12-1), 907 (CAS No. 71868-10-5). Under UV irradiation, a free radical initiator is added to crosslink and cure the polysiloxane to obtain the siloxane polymer. Under the irradiation of electron beam, the polysiloxane can be crosslinked and cured without adding free radical initiator to obtain the siloxane polymer.
Further, the initiator under the action of heat is at least one selected from Azodiisobutyronitrile (AIBN), azodiisoheptonitrile (ABVN), dimethyl Azodiisobutyrate (AIBME), azodiisobutylamidine hydrochloride (AIBA), azodiiso Ding Mi-in hydrochloride (AIBI), tert-butyl perbenzoate (TBPB), tert-butyl peracetate and ethyl 3, 3-di (tert-amyl peroxy) butyrate.
Further, the addition amount of the initiator is 0.05-1% of the mass of the crosslinkable modified polysiloxane.
The application uses a completely solvent-free reaction system, avoids the generation of organic waste liquid and the introduction of organic impurities, and is beneficial to environmental protection and cost reduction.
The application adopts the acid catalyst, and avoids the residue of the metal catalyst.
The synthesis method is optimized, the molecular weight of the polymer is controlled by the addition amount of the reaction control agent, the control agent is exhausted, and the reaction is stopped, so that compared with the prior art, the probability of sudden aggregation in the reaction process is reduced, meanwhile, the accuracy control of the molecular weight of the product is essentially improved, and the guarantee is provided for the repeatable production of the product.
According to the application, the siloxane oligomer and the crosslinkable silane coupling agent are premixed by optimizing the synthesis method, so that compared with the prior art, the siloxane oligomer and the crosslinkable silane coupling agent are mixed more fully, and the distribution of crosslinkable functional groups in the product is more uniform. The premixing is beneficial to improving the curing effect of the polysiloxane product in the subsequent application of generating the siloxane high polymer, so that the cured material has better structural uniformity, the processability is improved, and the wide application requirements are met.
Drawings
FIG. 1 shows HNMR spectra of a sample of example 2 of the present application.
Detailed Description
Terminology
In the present application, the following terms are used with the meanings defined below.
Copolymerization:
copolymerization is the polymerization reaction between silicon hydroxyl groups, between silicon alkoxy groups, between silicon hydroxyl groups and silicon alkoxy groups in the silicon unit-containing monomer.
Crosslinking:
crosslinking refers to the polymerization of reactive groups on the side chains of the unit monomers in the polysiloxane, which side chains refer to structures covalently attached to silicon atoms other than silicon hydroxyl groups and silicon alkoxy groups. Crosslinking is sometimes referred to herein as crosslinking curing or curing, i.e., occurs under thermally or radiation-catalyzed conditions, such as by adding a photoinitiator to the polysiloxane to cause polymerization by irradiation.
Crosslinkable functional groups:
the side chains of the monomer units forming the polysiloxane, which are covalently linked to silicon atoms in addition to the silicon hydroxyl groups and the silicon alkoxy groups, have active groups that can participate in the crosslinking reaction.
Alkyl:
refers to a branched or straight-chain saturated aliphatic hydrocarbon group having a specified number of carbon atoms. For example, "C1-C3 alkyl" means an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl), and pentyl (e.g., n-pentyl, isopentyl, neopentyl).
Polysiloxane:
the liquid substances obtained by copolymerization of monomers containing siloxane units are called polysiloxanes. Polysiloxanes are sometimes referred to herein as liquid polysiloxanes, crosslinkable modified polysiloxanes.
Siloxane polymers:
the solid material formed after curing the polysiloxane by crosslinking is called a siloxane polymer. The silicone polymers are sometimes referred to herein as solid silicone polymers, solid modified silicone polymers.
The application provides a solvent-free synthesis method of crosslinkable modified polysiloxane and a solid modified siloxane polymer. The liquid polysiloxane is obtained by copolymerizing specific unit monomers under the condition of completely containing no organic solvent through an optimized synthesis method, and then the siloxane high polymer with a net structure is formed by crosslinking and curing, so that a series of problems of organic solvent pollution, metal catalyst residues, precise control of polymer molecular weight, repeated production and the like in the synthesis process can be effectively solved.
In order to better illustrate the technical solution of the present application, the following specific examples are now provided.
Comparative example 1 preparation of a comparative sample of crosslinkable modified polysiloxane by the prior synthetic method
To a 2000ml three-necked flask was added 500g of hydroxy-terminated dimethyldiphenylpolysiloxane and 1000ml of toluene. One side of the three-necked bottle is connected with a water separator and is connected with a condenser pipe, mechanical stirring is added in the middle, and a thermometer is placed on the other side. The solution in the bottle was heated to reflux for 30 minutes and when a small amount of water was present in the water separator, a solution of stannous octoate catalyst (1.3 g in 100ml toluene) was added. Then 30g of acryloxypropyl trimethoxysilane was added dropwise for about 5 minutes. The condensation reaction took about 5 hours, immediately after which 30 ml of trimethylmethoxysilane was added as a terminator for the reaction. The reaction was stopped for 2 hours and then rapidly cooled to room temperature. The reaction mixture was poured into a 2000ml round-bottomed flask and spin-distilled at 70℃and 10mbar for 2h to finally give a crosslinkable modified polysiloxane, i.e.a comparative sample, in 520g yield.
EXAMPLE 1 solvent-free Cross-linkable modified polysiloxane sample 1
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 30g of acryloxypropyl dimethoxy silane, 0.6g of methanesulfonic acid and 40g of water are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator and connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is placed at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 10mbar at 60℃for 2h to finally give a solvent-free crosslinkable modified polysiloxane, sample 1, yield 524g, molecular weight Mw=43000, viscosity 11000cPs.
EXAMPLE 2 solvent-free Cross-linkable modified polysiloxane sample 2
500g of hydroxy-terminated dimethylpolysiloxane, 60g of methacryloxypropyl dimethoxy silane, 0.6g of trifluoromethanesulfonic acid and 40g of water are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator and connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is placed at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃at 5mbar for 2h, finally obtaining a solvent-free crosslinkable modified polysiloxane, sample 2, with a yield of 545g, a molecular weight Mw=45000 and a viscosity of 7900cPs.
EXAMPLE 3 solvent-free Cross-linkable modificationPolysiloxane sample 3
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 100g of methacryloxypropyl dimethoxy silane, 0.9g of benzenesulfonic acid and 40g of water are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator, a condenser is connected, mechanical stirring is added in the middle, and a thermometer is placed at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃and 10mbar for 2h, finally obtaining the solvent-free crosslinkable modified polysiloxane, sample 3, with a yield of 590g, a molecular weight Mw=44000 and a viscosity of 11300cPs.
EXAMPLE 4 solvent-free Cross-linkable modified polysiloxane sample 4
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 10g of methacryloxypropyl trimethoxysilane and 10g of 3-glycidoxypropyl trimethoxysilane are added into a 1000ml three-necked flask, 0.6g of methanesulfonic acid and 40g of water are added, one side of the three-necked flask is connected with a condenser through a water separator, mechanical stirring is added into the middle of the three-necked flask, and a thermometer is placed into the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃and 10mbar for 2h, finally obtaining the solvent-free crosslinkable modified polysiloxane, sample 4, with a yield of 501g, a molecular weight Mw=51000 and a viscosity of 13000cPs.
EXAMPLE 5 solvent-free Cross-linkable modified polysiloxane sample 5
500g of hydroxy-terminated dimethylpolysiloxane, 40g of methacryloxypropyl dimethoxy silane, 0.6g of methanesulfonic acid and 70g of acetic acid are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator and connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is arranged at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃and 10mbar for 2h, finally obtaining the solvent-free crosslinkable modified polysiloxane, sample 5, with a yield of 532g, a molecular weight Mw=42000 and a viscosity of 7800cPs.
EXAMPLE 6 solvent-free Cross-linkable modified polysiloxane sample 6
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 40g of 3-glycidoxypropyl trimethoxy silane, 0.6g of methanesulfonic acid and 60g of acetic acid are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator to be connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is arranged at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃and 10mbar for 2h, finally obtaining a solvent-free crosslinkable modified polysiloxane, sample 6, with yield 534g, molecular weight Mw=35000, viscosity 10300cPs.
EXAMPLE 7 solvent-free Cross-linkable modified polysiloxane sample 7
500g of hydroxy-terminated dimethylpolysiloxane, 40g of methacryloxypropyl dimethoxy silane, 0.6g of methanesulfonic acid and 50g of acetic acid are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator and connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is arranged at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and kept at the reaction temperature for 2h, the reaction was ended and naturally cooled to room temperature, the mixture was poured into a 1000ml round bottom flask and spin-distilled at 60℃and 10mbar for 2h, finally obtaining a solvent-free crosslinkable modified polysiloxane, sample 7, with a yield of 532g, a molecular weight Mw=29000 and a viscosity of 9500cPs.
EXAMPLE 8 solvent-free Cross-linkable modified polysiloxane sample 8
500g of hydroxy-terminated dimethylpolysiloxane, 40g of methacryloxypropyl dimethoxy silane, 0.6g of methanesulfonic acid and 80g of acetic acid are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator and connected with a condenser tube, mechanical stirring is added in the middle, and a thermometer is arranged at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and maintained at the reaction temperature for 2h, the reaction was cooled naturally to room temperature at the end, the mixture was poured into a 1000ml round bottom flask and steamed for 2h at 60℃at 10mbar. To neutralize the trace of acid catalyst in the product, 100ml of ethanol, 10g of calcium carbonate were added to a round bottom flask, after thorough stirring, the mixture was filtered, poured into a 1000ml round bottom flask, and spin-distilled at 70 degrees celsius at 10mbar for 2 hours, finally obtaining a solvent-free crosslinkable modified polysiloxane, sample 8, with a yield of 530g, molecular weight mw=53000, viscosity 13200cPs.
EXAMPLE 9 solvent-free Cross-linkable modified polysiloxane sample 9
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 100g of vinylmethyl dimethoxy silane, 0.9g of benzenesulfonic acid and 40g of water are added into a 1000ml three-necked flask, one side of the three-necked flask is connected with a water separator, a condenser is connected with the other side of the three-necked flask, mechanical stirring is added in the middle of the three-necked flask, and a thermometer is arranged on the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55deg.C, the reaction temperature was maintained for 2h, the reaction was cooled naturally to room temperature at the end of the reaction, and the mixture was poured into a 1000ml round bottom flask. To neutralize the trace of acid catalyst in the product, 100ml of ethanol, 10g of sodium carbonate are added into a round bottom flask, after being fully stirred, filtered, and then spin-steamed for 2 hours at 60 ℃ and 10mbar, finally obtaining solvent-free crosslinkable modified polysiloxane, namely sample 9, with yield of 578g, molecular weight Mw=33000 and viscosity of 9800cPs.
EXAMPLE 10 solvent-free Cross-linkable modified polysiloxane sample 10
500g of hydroxy-terminated dimethyl diphenyl polysiloxane, 80g of methacryloxypropyl dimethoxy silane and 20g of 3-aminopropyl methyl dimethoxy silane are added into a 1000ml three-necked flask, 0.9g of benzenesulfonic acid is added, 40g of water is added, one side of the three-necked flask is connected with a condenser tube by a water separator, mechanical stirring is added in the middle, and a thermometer is placed at the other side of the three-necked flask. After stirring thoroughly for 1h, the mixture was heated to 55℃and maintained at the reaction temperature for 2h, the reaction was cooled naturally to room temperature at the end, the mixture was poured into a 1000ml round bottom flask and steamed for 2h at 60℃at 10mbar. To neutralize the trace of acid catalyst in the product, 100ml of ethanol, 10g of calcium carbonate were added to a round bottom flask, after thorough stirring, the mixture was filtered, poured into a 1000ml round bottom flask, and spin-distilled at 70 degrees celsius at 10mbar for 2 hours, finally obtaining a crosslinkable modified polysiloxane, sample 10, with a yield of 549g, molecular weight mw=32000, viscosity 9500cPs.
The addition of an amount of initiator to the liquid polysiloxane allows for cross-linking cure under specific conditions.
50g of the prepared crosslinkable modified polysiloxane is added into a 500ml round bottom flask, an initiator is added, the addition amount is 0.05-1% of the mass of the crosslinkable modified polysiloxane, 100g of ethanol is added, the mixture is fully and uniformly stirred, the mixture is placed in a rotary evaporator, the water bath temperature is 50 ℃, the rotating speed is 60rpm, the vacuum degree is regulated to 10mbar, and the mixture is subjected to rotary evaporation treatment for 1h, so that a sample with the initiator is obtained.
And (3) coating the sample added with the initiator on the surface of the PET film by using a knife coating machine, wherein the thickness of the coating is 100 micrometers, covering a layer of PET on the upper surface, performing photo-curing, and placing the sample in a UV lamp box to receive irradiation for 30 seconds or performing thermal curing, and placing the sample in an oven for 30 minutes. If electron beam curing is used, the curing time is 30s and the initiator does not have to be added.
And (3) performing curing verification according to the respective initiation conditions, and confirming the curing effect. The cured sample is scraped and weighed, fully soaked in ethanol solution and sonicated for 24 hours, liquid and residual solids are separated by filtration, the weight loss of the residual solids is calculated, if the weight loss is greater than 10%, the curing is considered insufficient, and if the weight loss is less than 10%, the curing is confirmed to be sufficient. The crosslinking curing results of the comparative and example samples are shown in Table 1.
TABLE 1 crosslinking curing results for comparative and example samples
From the results of Table 1, it can be seen that by selecting an appropriate initiator system according to the nature of the crosslinking groups in the crosslinkable silane coupling agent monomer, all samples can be completely cured with an initiator mass of between 0.05% and 1% of the mass of the crosslinkable modified polysiloxane, i.e., the polysiloxane prepared using solvent-free conditions can achieve the same curing effect as the polysiloxane material prepared in an organic solvent system. Of course, those skilled in the art will appreciate that the initiator mass may be present in excess of 1% by mass of the crosslinkable modified polysiloxane without significantly affecting the degree of cure, and that the initiator mass is preferably present in an amount of between 0.05% and 1% by mass of the crosslinkable modified polysiloxane for economic reasons.
FIG. 1 is a HNMR plot of the solvent-free polysiloxane sample prepared in example 2, showing clearly the characteristic peaks of two H's on the methacryloxy double bond at chemical shifts of 6.02ppm and 5.47ppm, from which the content of crosslinkable modifying groups can be determined, also demonstrating that the crosslinkable silane coupling agent monomer, i.e., methacryloxypropyl dimethoxy silane, has polymerized onto the crosslinkable modified polysiloxane molecular chain.
The solvent-free crosslinkable modified polysiloxane provided by the application can be applied to various technological processes for manufacturing products through curing, such as packaging systems of chips, LED lamps, solar power generation and the like, and can also be applied to 3D printing systems, photo-curing/thermosetting film forming systems, such as electrochromic films, optical films, infrared barrier films and the like.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A solvent-free synthesis method of a crosslinkable modified polysiloxane, characterized in that an organic solvent is not used in the synthesis process, comprising the following steps:
premixing: uniformly mixing 100 parts by mass of siloxane oligomer, 1-20 parts by mass of crosslinkable silane coupling agent monomer, 0.1-5 parts by mass of acid catalyst and 1-10 parts by mass of reaction control agent; the siloxane oligomer is one or more of hydroxyl end-capped siloxane oligomer and methoxy end-capped siloxane oligomer; the crosslinkable silane coupling agent monomer is one or more of an aminosilane coupling agent monomer, a vinyl silane coupling agent monomer, a methacryloxy silane coupling agent monomer and an acryloxy silane coupling agent monomer; the acid catalyst is one or more of sulfuric acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and fluorosulfonic acid; the reaction control agent is water and/or acetic acid;
the reaction: and heating the premixed mixture to 40-80 ℃ for reaction for 1-10 h, and distilling off low-boiling substances at the vacuum degree of less than 10mbar after the reaction is finished to obtain the crosslinkable modified polysiloxane.
2. A crosslinkable modified polysiloxane, characterized in that it is synthesized by the method of claim 1; the main chain is siloxane, and the side chain contains at least one crosslinkable functional group, and its structure can be shown in the following figure
Wherein,
R 1 is one or more of hydrogen, alkyl, alkoxy and aromatic groups;
R 2 is a crosslinkable functional group selected from one or more of vinyl, amino, acryloyloxy, methacryloyloxy; the content of the crosslinkable functional group is 0.1% -20% of the total mass of the polysiloxane;
R 3 is one or more of hydrogen, hydroxyl and methoxy;
n=a positive integer of 1 to 100,000, and m=a positive integer of 1 to 10,000.
3. A crosslinkable modified polysiloxane according to claim 2, characterized in that the polysiloxane has a molecular weight mn=1000 to 100,000 and a viscosity of 500 to 50,000cps.
4. A solid modified siloxane polymer is characterized in that the crosslinkable modified polysiloxane is obtained by crosslinking and curing reaction under the initiation of an initiator under the action of light and/or heat.
5. A solid modified silicone polymer as set forth in claim 4, wherein said light action is UV light irradiation.
6. A solid modified silicone polymer according to claim 4, wherein the thermal action is heating the crosslinkable modified polysiloxane to a temperature of 40 ℃ to 80 ℃.
7. The solid modified silicone polymer of claim 4, wherein the initiator is a cationic initiator selected from at least one of sulfonium salts, aryldiazonium salts, diarylhalonium salts, and triarylhalonium salts.
8. The solid modified silicone polymer of claim 4, wherein the initiator is a free radical initiator selected from at least one of 184 (CAS No. 947-19-3), ITX (CAS No. 5495-84-1 or 83846-86-0), 819 (CAS No. 162881-26-7), 1173 (CAS No. 7473-98-5), BDK (CAS No. 24650-42-8), BP (CAS No. 119-61-9), TPO (CAS No. 75980-60-8), 369 (CAS No. 119313-12-1), 907 (CAS No. 71868-10-5).
9. The solid modified silicone polymer according to claim 4, wherein the initiator is added in an amount of 0.05 to 1% by mass of the crosslinkable modified polysiloxane.
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| CN108913023A (en) * | 2018-06-13 | 2018-11-30 | 北京化工大学 | A kind of preparation method of ultraviolet curing acrylic ester polysiloxanes clear coat |
| CN112480816A (en) * | 2020-11-30 | 2021-03-12 | 山东东岳有机硅材料股份有限公司 | Room-temperature-curing solvent-free conformal coating and preparation method thereof |
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| CN108913023A (en) * | 2018-06-13 | 2018-11-30 | 北京化工大学 | A kind of preparation method of ultraviolet curing acrylic ester polysiloxanes clear coat |
| CN112480816A (en) * | 2020-11-30 | 2021-03-12 | 山东东岳有机硅材料股份有限公司 | Room-temperature-curing solvent-free conformal coating and preparation method thereof |
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