WO2019178873A1 - 氟硅树脂及其制备方法 - Google Patents
氟硅树脂及其制备方法 Download PDFInfo
- Publication number
- WO2019178873A1 WO2019178873A1 PCT/CN2018/080358 CN2018080358W WO2019178873A1 WO 2019178873 A1 WO2019178873 A1 WO 2019178873A1 CN 2018080358 W CN2018080358 W CN 2018080358W WO 2019178873 A1 WO2019178873 A1 WO 2019178873A1
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- WIPO (PCT)
- Prior art keywords
- pentafluorophenethyldimethylchlorosilane
- reaction
- fluorosilicone resin
- mixture
- distilled
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 38
- ONRUBMJWAATKFA-UHFFFAOYSA-N chloro-dimethyl-[2-(2,3,4,5,6-pentafluorophenyl)ethyl]silane Chemical compound C[Si](C)(Cl)CCC1=C(F)C(F)=C(F)C(F)=C1F ONRUBMJWAATKFA-UHFFFAOYSA-N 0.000 claims abstract description 35
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 16
- 239000005048 methyldichlorosilane Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- -1 phenethyl dimethyl chloroguanidine Chemical compound 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Chemical group 0.000 claims description 4
- 229910052739 hydrogen Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Chemical group 0.000 claims description 3
- QDZIRNXWFDZVBD-UHFFFAOYSA-N 1-chloro-3,3-dimethyl-1-[2-(2,3,4,5,6-pentafluorophenyl)ethyl]guanidine Chemical compound FC1=C(C(=C(C(=C1CCN(C(=N)N(C)C)Cl)F)F)F)F QDZIRNXWFDZVBD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- NTQLJFJHPPAPKV-UHFFFAOYSA-N chloro(2-methylprop-1-enyl)silane Chemical compound CC(C)=C[SiH2]Cl NTQLJFJHPPAPKV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- 229920002050 silicone resin Polymers 0.000 abstract description 20
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000005046 Chlorosilane Substances 0.000 abstract description 2
- PQRFRTCWNCVQHI-UHFFFAOYSA-N chloro-dimethyl-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound C[Si](C)(Cl)C1=C(F)C(F)=C(F)C(F)=C1F PQRFRTCWNCVQHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 23
- 229910000077 silane Inorganic materials 0.000 description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 20
- 229920001296 polysiloxane Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000000284 extract Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000012265 solid product 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000007719 peel strength test Methods 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000013464 silicone adhesive Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical compound Cl[SiH2]C=C DMZWVCJEOLBQCZ-UHFFFAOYSA-N 0.000 description 1
- NBWIIOQJUKRLKW-UHFFFAOYSA-N chloro(phenyl)silane Chemical compound Cl[SiH2]C1=CC=CC=C1 NBWIIOQJUKRLKW-UHFFFAOYSA-N 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C08G77/06—Preparatory processes
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/44—Sulfenamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Definitions
- the present invention relates to a high temperature resistant fluorosilicone resin and a preparation method thereof, and the produced product can be used as a polymer modification or polymer additive, and belongs to the field of organosilicon synthesis and polymer auxiliaries.
- Silicone is a thermosetting plastic. One of its most outstanding properties is its excellent thermal oxidation stability and excellent electrical insulation properties. It maintains its good insulation properties over a wide temperature and frequency range. .
- the silicone resin is usually a mixture of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane in the presence of an organic solvent such as toluene. , adding water at a lower temperature to obtain an acidic hydrolyzate.
- the initial product of hydrolysis is a mixture of cyclic, linear and crosslinked polymers, usually containing a substantial amount of hydroxyl groups.
- the hydrolyzate is washed with water to remove acid, neutral condensate, thermally oxidized in air or further polycondensed in the presence of a catalyst, and finally forms a highly crosslinked stereo network structure.
- MQ resin is one of the most widely used silicone resins, which consists of a monofunctional silicon oxide unit (referred to as M unit).
- a tetrafunctional siloxy unit consisting of a compact sphere with a two-layer structure, the molar mass of which is generally 1000-8000 g, the ratio of the M chain to the Q link in the molecular structure and M
- the structure determines the nature of the MQ resin.
- the most common M structure is methyl.
- the introduction of other groups in the MQ silicone resin can expand its use, but after introducing other structures into the MQ silicone resin, since these structures are reactive under certain conditions, it is disadvantageous to the heat resistance of the silicone resin; even if benzene is introduced
- the silicone resin of the base M structure also undergoes a mass loss of up to 8% after heating at 250 ° C for 24 hours. This limits its use as a composite component at temperatures above 250 °C.
- the present invention provides a novel silicone resin and a preparation method thereof, in view of the disadvantages of the existing silicone resin which has insufficient heat resistance.
- a fluorosilicone resin the chemical structural formula of the fluorosilicone resin is:
- R methyl, phenyl, vinyl or hydrogen
- the method for preparing the fluorosilicone resin includes the following steps:
- the mass ratio of pentafluorostyrene, noble metal salt, and methyldichlorosilane is 1: (0.003 to 0.006): (0.5 to 2); pentafluorophenethyldimethylchlorosilane and In the mixture of tetraethyl orthosilicate, the mass ratio of pentafluorophenethyldimethylchlorosilane to ethyl orthosilicate is (1 to 6): (1-10); trihydrocarbyl monochlorosilane and orthosilicate In the mixture of ethyl esters, the mass ratio of trihydrocarbyl monochlorosilane to ethyl orthosilicate is (1 to 3): (1 to 10).
- the step (1) is: dissolving pentafluorostyrene in an aromatic hydrocarbon solvent, adding a noble metal salt catalyst under nitrogen protection; and then adding methyldichlorosilane at 50 to 140 ° C After the completion of the dropwise addition, the reaction is incubated for 1 to 10 hours to prepare penta-gas phenethyl dimethyl chlorin;
- Step (2) is: dispersing water and inorganic acid in an organic solvent, and then adding a mixture of pentafluorophenethyldimethylchlorosilane and tetraethyl orthosilicate at 60 to 80 ° C, After the addition is completed, the polycondensation is carried out once for 0.5 to 1 hour; then, a mixture of trihydrocarbylmonochlorosilane and tetraethyl orthosilicate is added dropwise, and after the completion of the dropwise addition, the polycondensation reaction is further carried out for 1 to 6 hours to prepare a fluorosilicone resin.
- the aromatic hydrocarbon solvent is one of toluene, xylene, trifluorotoluene, 1,3 -bis(trifluoromethyl)benzene;
- the noble metal salt is chloroplatinic acid;
- the trihydrocarbyl monochlorosilane is one of trimethylchlorosilane, dimethylhydrogen monochlorosilane, dimethylvinylmonochlorosilane, phenyldimethylchlorosilane;
- the inorganic acid is Concentrated sulfuric acid or concentrated hydrochloric acid;
- the organic solvent is tetrahydrofuran.
- step (1) the time of adding methyldichlorosilane is 0.5 ⁇ 5 hours; in step (2), the time of adding the mixture of trihydrocarbylmonochlorosilane and tetraethyl orthosilicate is added dropwise. It is 0.5 ⁇ 1 hour.
- reaction liquid is distilled off and distilled under reduced pressure to obtain pentafluorophenethyldimethylchlorosilane; Step (2) After the polycondensation reaction is completed, the reaction liquid passes through Cooling, vacuum distillation, liquid separation treatment, extraction, washing with distilled water, drying, filtration, and distillation to obtain a fluorosilicone resin.
- the present invention also discloses a pentafluorophenethyldimethylchlorosilane and a preparation method thereof, comprising the steps of: dissolving pentafluorostyrene in an aromatic hydrocarbon solvent, and adding a noble metal salt catalyst under nitrogen protection; Then, methyldichlorosilane is added dropwise at 50 to 140 ° C; after the completion of the dropwise addition, the reaction is kept for 1 to 10 hours to prepare pentafluorobenzene. Ethyldimethylchlorosilane.
- the aromatic hydrocarbon solvent is one of toluene, xylene, trifluorotoluene, 1,3 - bis (trifluoromethyl) benzene;
- the noble metal salt is chloroplatinic acid;
- the time for dropwise addition of methyldichlorosilane is: After the reaction is completed, the reaction liquid is distilled off and distilled under reduced pressure to obtain pentafluorophenethyldimethylchlorosilane.
- the present invention comprises a method for synthesizing a silicone resin by polycondensation reaction of pentafluorophenethyldimethylchlorosilane with tetraethyl orthosilicate or monochlorosilane monomer, and the reaction formula is as follows:
- R methyl, phenyl, vinyl or hydrogen.
- the synthetic step of the fluorosilicone resin comprises a two-step reaction of hydrosilylation and polycondensation into a silicone resin, and the specific steps can be as follows:
- the present invention uses pentafluorostyrene and dimethylmonochlorosilane as raw materials to synthesize pentafluorophenethyldimethylchlorosilane by hydrosilylation reaction, and then pentafluorophenethyldimethylchlorosilane , trimethylchlorosilane, tetraethyl orthosilicate copolycondensation, using a secondary polycondensation process to prepare a fluorosilicone resin.
- the pentafluorobenzene fluorosilicone resin of the invention has better thermal stability, high fluorocarbon bond energy and excellent heat resistance, and is heated at 550 ° C and 400 atm for 24 hours. It is not decomposed and can be used as a fluorosilicone material with excellent heat resistance. It is suitable for use as a high temperature resistant additive in a variety of composite systems.
- the fluorosilicone resin disclosed in the present invention is different from the prior art modified silicone resin in that the fluorine-containing silicone resin provided by the present invention has a large planar structure and a fluorocarbon bond energy due to phenyl conjugate. Thus, a silicone material excellent in heat resistance is provided.
- the stepwise polycondensation process is creatively solved because the pentafluorophenyl group in pentafluorophenethyldimethylchlorosilane is a rigid group and has a large steric hindrance.
- the difference in reactivity between the two monochlorosilanes caused by the difference in hydrolysis reactivity compared to the trihydrocarbylmonochlorosilane monomer avoids excessive crosslinking, thereby producing a high yield of fluorosilicone resin of 70% to 80% ;
- the fluorosilicone resin is realized by a polycondensation reaction, and there is an extraction operation in the preparation, and the general yield is low.
- the fluorine content of the fluorosilicone resin provided by the invention is adjustable, thereby improving the designability of the heat resistant product; and the raw materials used in the preparation of the fluorosilicone resin of the invention are all commercially available raw materials, the source is wide, and the price is low. , is conducive to the industrial production of materials.
- Example 1 is an infrared spectrum diagram of a fluorosilicone resin prepared in Example 1;
- Example 2 is a graph showing the results of thermal weight loss test of the fluorosilicone resin prepared in Example 1.
- 80 g of toluene and 65 g of pentafluorostyrene were successively added, stirred and dissolved, and 0.26 g of a chloroplatinic acid catalyst was added under a nitrogen atmosphere.
- the heating was turned on, and after heating to 80 ° C, 51 g of methyldichlorohydrosilane was added dropwise, and the dropping time was controlled to about 1 hour. After the addition was completed, the reaction was continued for 2 hours.
- the reaction is stopped, and the reaction liquid is first distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran, and the distillation temperature is The temperature was 60 ° C, the degree of vacuum was 10 mmHg, and it was distilled until no liquid was distilled off.
- the toluene was extracted three times, and the amount of toluene used each time was 30 g.
- the extracts were combined and washed 5 times with distilled water, using 15 g of distilled water each time. After the end of the washing, 6 g of anhydrous sodium sulfate was added and dried for 5 hours.
- the desiccant was removed by filtration, and distilled to obtain 36.3 g of a white solid solid fluorophenyl silicone resin at a temperature of 80 ° C and a vacuum of 0.5 mmHg. The yield was 72.6%.
- FIG. 1 The infrared spectrum curve of the fluorosilicone resin prepared above is shown in FIG. 1; it can be seen from the figure that a characteristic absorption peak of the benzene ring skeleton appears at 1620 cm -1 , and 2960 cm -1 is -CH 3
- 1410 cm -1 is the weak asymmetric deformation vibration of CH in -CH 3
- 1260 cm -1 is caused by the in-plane and out-of-plane bending vibration of Si-CH 3 group -CH 3
- 1100 to 1020 cm -1 is a Si-0-Si stretching vibration absorption peak
- 804 cm is a Si-C stretching vibration absorption peak.
- thermogravimetric test results of the above-prepared high temperature resistant fluorosilicone resin are shown in FIG. 2; the results show that the resin is heated to 394 ° C, 5% mass loss occurs, and the carbon residue rate reaches 19.8%, which indicates that the fluorine-containing phenyl group Silicone resin has very excellent heat resistance.
- the reaction was stopped, and the reaction liquid was distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
- the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
- the toluene was extracted three times, and the amount of toluene used each time was 30 g.
- the extracts were combined and washed 5 times with distilled water, using 15 g of distilled water each time. After the end of the washing, it was further dried by adding 6 g of anhydrous sodium sulfate for 5 hours.
- the desiccant was removed by filtration, and distilled to obtain a white loose solid product fluorosilicone resin 41.6 g at a temperature of 80 ° C and a vacuum of 0.5 mmHg, yielding a yield of 83.2%.
- DBTL dibutyltin dilaurate
- the chloroplatinic acid catalyst O. lg was added by adding 40 g of trifluoromethylbenzene and 32 g of pentafluorostyrene. The heating was turned on, and after heating to 80 ° C, 26 g of methyldichlorohydrosilane was added dropwise, and the dropping time was controlled to about 1 hour. After the addition, the reaction was continued for 1.5 hours.
- the reaction was stopped, and the reaction liquid was distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
- the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
- the toluene was extracted three times, and the amount of toluene used each time was 30 g.
- the extracts were combined and washed 5 times with distilled water, using 15 g of distilled water each time. After the end of the washing, it was further dried by adding 6 g of anhydrous sodium sulfate for 5 hours.
- the desiccant was removed by filtration, and distilled to obtain a white loose solid product of pentafluorophenylvinyl silicone resin (34.1 g) at a temperature of 80 ° C and a vacuum of 0.5 mmHg, yielding a yield of 68.2%.
- DBTL dibutyltin dilaurate
- the reaction was stopped, and the reaction liquid was distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
- the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
- the mixture was extracted three times with xylene, and the amount of xylene used each time was 30 g.
- the extracts were combined and washed 5 times with distilled water, using 15 g of distilled water each time. After the completion of the washing, it was further dried by adding 6 g of anhydrous magnesium sulfate for 5 hours.
- the leaching agent was removed by filtration to give a white solid solid product fluorosilicone resin (33.8 g, yield: 67.6%).
- DBTL dibutyltin dilaurate
- the reaction was stopped, and the reaction liquid was distilled under reduced pressure to remove by-product ethanol and solvent tetrahydrofuran.
- the distillation temperature was 60 ° C, the degree of vacuum was 10 mmHg, and distillation was carried out until no liquid was distilled off.
- the toluene was extracted three times, and the amount of toluene used per time was 25 g.
- the extracts were combined and washed 5 times with distilled water, using 12 g of distilled water each time. After the end of the washing, 5 g of anhydrous sodium sulfate was added and dried for 5 hours.
- the desiccant was removed by filtration, and distilled to obtain 35.6 g of a white solid solid product of pentafluorophenyl vinyl silicone resin at a temperature of 80 ° C and a vacuum of 0.5 mmHg, and the yield was 71.2%.
- DBTL dibutyltin dilaurate
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Abstract
提供了一种氟硅树脂及其制备方法。以五氟苯乙烯为原料,通过硅氢加成反应得到五氟苯乙基二甲基氯硅烷。利用五氟苯乙基二甲基氯硅烷与三甲基氯硅烷、正硅酸乙酯进行缩聚反应,制备一种五氟苯基硅树脂。制备时采用二次缩聚工艺,克服了五氟苯基二甲基氯硅烷与共聚的三烃基一氯硅烷水解反应性差异大的缺陷,制备收率高。得到的五氟苯基硅树脂耐热性优越,具有制备工艺简单,对设备要求低,原材料易得,适合工业化放大生产的优点。耐热型氟硅树脂可应用于耐热型胶粘剂等高分子材料。
Description
发明名称:氟硅树脂及其制备方法
技术领域
[0001] 本发明涉及一种耐高温型氟硅树脂及其制备方法, 生产的产物可用作高分子改 性或高分子添加剂, 属于有机硅合成和高分子助剂领域。
背景技术
[0002] 硅树脂是一种热固性的塑料, 其最突出的性能之一是优异的热氧化稳定性和优 异的电绝缘性能, 它在宽的温度和频率范围内均能保持其良好的绝缘性能。 硅 树脂通常是用甲基三氯硅烷、 二甲基二氯硅烷、 苯基三氯硅烷、 二苯基二氯硅 烷或甲基苯基二氯硅烷的各种混合物, 在有机溶剂如甲苯存在下, 在较低温度 下加水分解, 得到酸性水解物。 水解的初始产物是环状的、 线型的和交联聚合 物的混合物, 通常还含有相当多的羟基。 水解物经水洗除去酸、 中性的初缩聚 体, 于空气中热氧化或在催化剂存在下进一步缩聚, 最后形成高度交联的立体 网络结构。
[0003] MQ树脂是应用最广泛的硅树脂之一, 其由单官能度的硅氧单元 (简称 M单元
) 和四官能度的硅氧单元 (简称 Q单元) 组成的一种具有双层结构的紧密球状物 , 其摩尔质量一般为 1000-8000g, 分子结构中 M链节与 Q链节之比及 M的结构决 定了 MQ树脂的性质, 最常见的 M结构为甲基。 在 MQ硅树脂中引入其他基团可 以扩展其用途, 但是在 MQ硅树脂中引入其他结构后, 由于这些结构在一定条件 下具有反应性, 因此不利于硅树脂耐热性能; 即便是引入了苯基 M结构的硅树脂 , 其在 250°C加热 24小时后也会发生高达 8%的质量损失。 这限制了其在高于 250 °C温度条件下作为复合材料组分的使用。
发明概述
技术问题
[0004] 本发明针对现有的有机硅树脂存在的耐热性能不足的缺点, 提供一种新的有机 硅树脂及其制备方法。
问题的解决方案
技术解决方案
[0005] 为达到本发明所述的发明目的, 采用的技术方案如下:
[0006] 一种氟硅树脂, 所述氟硅树脂的化学结构式为:
[0007] 其中, R=甲基、 苯基、 乙烯基或氢;
[0008] m=2〜 20; n=l〜 5; p=l〜 8。
[0009] 上述氟硅树脂的制备方法, 包括如下步骤:
[0010] (1) 以五氟苯乙烯、 甲基二氯硅烷为原料, 在贵金属盐催化下, 制备五氟苯
乙基—甲基氯桂焼;
[0011] (2) 将五氟苯乙基二甲基氯硅烷与正硅酸乙酯的混合物滴加入 7jc/无机酸 /有机 溶剂的混合液中进行一次缩聚反应; 然后再滴加三烃基一氯硅烷与正硅酸乙酯 的混合物, 再次缩聚反应后, 制备氣桂树脂。
[0012] 上述技术方案中, 五氟苯乙烯、 贵金属盐、 甲基二氯硅烷的质量比为 1: (0.003 〜 0.006) : (0.5〜 2) ; 五氟苯乙基二甲基氯硅烷与正硅酸乙酯的混合物中, 五 氟苯乙基二甲基氯硅烷与正硅酸乙酯的质量比为 (1〜 6) : (1-10) ; 三烃基一 氯硅烷与正硅酸乙酯的混合物中, 三烃基一氯硅烷与正硅酸乙酯的质量比为 (1 〜 3) : (1〜 10) 。
[0013] 上述技术方案中, 步骤 (1) 为, 将五氟苯乙烯溶解于芳香烃类溶剂中, 氮气 保护下加入贵金属盐催化剂; 然后于 50〜 140°C下滴加甲基二氯硅烷; 滴加完成 后保温反应 1~ 10小时, 制备五氣苯乙基二甲基氯桂焼;
[0014] 步骤 (2) 为, 将水、 无机酸分散在有机溶剂中, 然后于 60〜 80°C下滴加五氟 苯乙基二甲基氯硅烷与正硅酸乙酯的混合物, 滴加完成后保温进行一次缩聚 0.5 〜 1小时; 然后再滴加三烃基一氯硅烷与正硅酸乙酯的混合物, 滴加完成后保温 进行再次缩聚反应 1〜 6小时, 制备氟硅树脂。
[0015] 上述技术方案中, 所述芳香烃类溶剂为甲苯、 二甲苯、 三氟甲苯、 1,3 -双 (三 氟甲基) 苯中的一种; 所述贵金属盐为氯铂酸; 所述三烃基一氯硅烷为三甲基 氯硅烷、 二甲基氢基一氯硅烷、 二甲基乙烯基一氯硅烷、 苯基二甲基一氯硅烷 中的一种; 所述无机酸为浓硫酸或者浓盐酸; 所述有机溶剂为四氢呋喃。
[0016] 上述技术方案中, 步骤 ⑴ 中, 滴加甲基二氯硅烷的时间为 0.5〜 5小时; 步骤 (2) 中, 滴加三烃基一氯硅烷与正硅酸乙酯的混合物的时间为 0.5~1小时。
[0017] 上述技术方案中, 步骤 (1) 反应结束后, 反应液经过蒸除、 减压蒸馏得到五 氟苯乙基二甲基氯硅烷; 步骤 (2) 再次缩聚反应结束后, 反应液经过冷却、 减 压蒸馏、 分液处理、 萃取、 蒸馏水洗涤、 干燥、 过滤、 蒸馏得到氟硅树脂。
[0018] 本发明还公开了一种五氟苯乙基二甲基氯硅烷及其制备方法, 包括以下步骤, 将五氟苯乙烯溶解于芳香烃类溶剂中, 氮气保护下加入贵金属盐催化剂; 然后 于 50〜 140°C下滴加甲基二氯硅烷; 滴加完成后保温反应 1〜 10小时, 制备五氟苯
乙基二甲基氯硅烷。
[0019] 上述技术方案中, 所述芳香烃类溶剂为甲苯、 二甲苯、 三氟甲苯、 1,3 -双 (三 氟甲基) 苯中的一种; 所述贵金属盐为氯铂酸; 滴加甲基二氯硅烷的时间为; 反应结束后, 反应液经过蒸除、 减压蒸馏得到五氟苯乙基二甲基氯硅烷。
[0020] 本发明通过五氟苯乙基二甲基氯硅烷与正硅酸乙酯、 一氯硅烷单体通过缩聚反 应合成硅树脂的方法, 其反应式如下:
[0021]
[]
[0022] 其中, R =甲基、 苯基、 乙烯基或氢。
[0023] 根据上述技术方案, 氟硅树脂的合成步骤包括硅氢加成与缩聚合成硅树脂两步 反应, 具体步骤可以如下:
[0024] ( 1) 硅氢加成反应
[0025] 按重量计, 将 1份五氟苯乙烯溶解于 1〜 10份芳香烃类溶剂中, 氮气保护下加入 氯铂酸催化剂 0.003~0.006份, 加热至 50~140°C后, , 于一定时间内滴加 0.5~2份 甲基二氯硅烷, 滴加完后继续保温反应 1~10小时。 反应结束后, 蒸除溶剂和未 反应的甲基二氯硅烷, 减压蒸馏收集 132°C馏分 (3.75kPa) , 得五氟苯乙基二甲 基氯桂焼;
[0026] (2) 混合硅烷: 按重量计, 将 1~6份五氟苯乙基二甲基氯硅烷与 1~10份正硅酸 乙酯混合, 得到混合硅烷一。 按重量计, 将 1~3份三烃基一氯硅烷与 1~10份正硅 酸乙酯混合, 得到混合硅烷二;
[0027] (3) 一次缩聚反应: 按重量计, 将 1~5份水和 0.5~2份无机酸分散在 1~20份四
氢呋喃中, 加热使混合物温度升至 60~80°C后, 滴加上述混合硅烷一, 滴加时间 以反应液温度不超过 80°C为准, 加完后保温反应 0.5~1小时;
[0028] (4) 二次缩聚反应: 一次缩聚结束后, 再慢速加入混合硅烷二, 滴加时间为 0.
5~1小时, 加完后保温反应 1~6小时;
[0029] (5) 后处理: 将反应液冷却后, 减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为 40〜 80°C, 真空度为 0.5〜 20_Hg。 将蒸馏后剩余的反应液倒入 分液漏斗, 用萃取剂萃取 3~5次, 每次使用萃取剂 1~5份。 合并萃取液, 以蒸馏 水洗涤 3~5次, 每次使用 1~5份蒸馏水。 再加入 0.2~1份干燥剂干燥 0.5~5小时。 过 滤除去干燥剂, 蒸馏得到白色的松散固体产物氟硅树脂, 蒸馏的温度为 40〜 80°C , 真空度为 0.5〜 20mmHg。
[0030] 本发明以五氟苯乙烯和二甲基一氯硅烷为原料, 通过硅氢加成反应合成五氟苯 乙基二甲基氯硅烷, 再将五氟苯乙基二甲基氯硅烷、 三甲基氯硅烷、 正硅酸乙 酯共缩聚, 采用二次缩聚工艺, 制备一种氟硅树脂。 与现有树脂相比, 本发明 的五氟苯氟硅树脂具有更好的热稳定性, 碳氟键键能高、 耐热性更优异, 其在 3 50°C及 400大气压下加热 24小时不分解, 可用作构筑耐高温材料, 将获得耐热性 能非常优异的氟硅树脂材料, 这些材料适合作为耐高温添加剂应用于多种复合 材料体系。
发明的有益效果
有益效果
[0031] 本发明与现有技术相比的突出优点是:
[0032] 1、 本发明公开的氟硅树脂, 与现有技改性术硅树脂中不同的是, 本发明提供 的含氟硅树脂由于苯基共轭的平面结构以及碳氟键键能大, 由此提供了一种耐 热性能优越的有机硅材料。
[0033] 2、 本发明公开的氟硅树脂制备过程中, 创造性的采用分步缩聚工艺解决了由 于五氟苯乙基二甲基氯硅烷中五氟苯基为刚性基团、 位阻大, 水解反应性比三 烃基一氯硅烷单体差导致的两种一氯硅烷的反应性差异, 避免过度交联, 由此 制备氟硅树脂收率高, 到 70%~80% ; 解决了现有氟硅树脂由缩聚反应实现, 且 制备中有萃取操作, 一般收率都较低的问题。
[0034] 3、 本发明提供的氟硅树脂中氟含量可调, 从而提高耐热产物的可设计性; 而 且本发明制备氟硅树脂所使用的原材料均为市售原料, 来源广泛, 价格便宜, 有利于材料的工业化生产。
对附图的简要说明
附图说明
[0035] 图 1是实施例一制备的氟硅树脂的红外光谱图;
[0036] 图 2是实施例一制备的氟硅树脂的热失重测试结果图。
发明实施例
本发明的实施方式
[0037] 下面结合附图和实施例对本发明技术方案作进一步的阐述。
[0038] 实施例一
[0039] ( 1) 五氟苯乙基二甲基氯硅烷合成
[0040] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 依次 加入 80g甲苯和 65g五氟苯乙烯, 搅拌溶解, 氮气保护下加入氯铂酸催化剂 0.26g 。 开启加热, 升温至 80°C后, 滴加 51g甲基二氯氢硅烷, 滴加时间控制在 1小时左 右。 滴加完后继续保温反应 2小时。 反应结束后, 蒸除溶剂和未反应的甲基二氯 硅烷, 减压蒸馏收集 132°C馏分 (3.75kPa) , 得五氟苯乙基二甲基氯硅烷 95g, 气相色谱测得产物纯度为 96.6%, 收率 90.9%。
[0041] (2) 缩聚合成氟硅树脂
[0042] 在 100mL锥形瓶中将 19.4g五氟苯乙基二甲基氯硅烷和 33g正硅酸乙酯混合均匀 , 得到混合硅烷一; 另取一 100mL锥形瓶中将 5.5g三甲基一氯硅烷和 30g正硅酸 乙酯混合均匀, 得到混合硅烷二。 两种混合硅烷备用。
[0043] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 先将
8g水和 5g浓硫酸小心缓慢键入 50g四氢呋喃中, 加热使混合物温度升至 70°C后, 滴加上述预先配好的混合硅烷一, 滴加时间控制在 45min左右。 加完后, 保温反 应 0.5~1小时。 然后继续滴加混合硅烷二, 滴加时间为 1小时, 加完后, 二次缩聚 , 反应 6小时。
[0044] 停止反应, 反应液先减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为
60°C, 真空度为 lOmmHg, 蒸馏至无液体馏出为止。 甲苯萃取 3次, 每次使用甲 苯量为 30g。 合并萃取液, 以蒸馏水洗涤 5次, 每次使用 15g蒸馏水。 洗涤结束后 , 再加入 6g无水硫酸钠干燥 5小时。 过滤除去干燥剂, 于温度为 80°C、 真空度为 0 .5mmHg条件下蒸馏得到白色的松散固体产物含氟苯基硅树脂 36.3g, 收率为 72.6 %。
[0045] 上述制备的氟硅树脂的红外光谱曲线见附图 1 ; 从图中可以看到, 1620cm - 1处 出现了苯环骨架的特征吸收峰, 2960cm - 1为 -CH 3
中 C-H伸缩振动吸收峰, 1410cm - 1为 -CH 3中 C-H的弱不对称变形振动, 1260cm -1 为 Si-CH 3基的 -CH 3面内和面外弯曲振动引起的。 1100〜 1020cm -1为 Si-0-Si伸缩 振动吸收峰, 804cm 为 Si-C伸缩振动吸收峰。
[0046] 上述制备的耐高温氟硅树脂的热失重测试结果见附图 2; 结果表明, 树脂加热 至 394°C出现 5%质量损失, 且残炭率达到 19.8%, 这说明含氟苯基硅树脂具有非 常优异的耐热性。
[0047] 产物氟硅树脂分子结构如下:
[]
[0048] 其中, m =2〜 10; n =l~3; p=l~3。
[0049] 实施例二
[0050] ( 1) 五氟苯乙基二甲基氯硅烷合成工艺同实施例一。
[0051] (2) 缩聚合成氟硅树脂
[0052] 在 250mL锥形瓶中将 19.4g五氟苯乙基二甲基氯硅烷、 5.5g三甲基一氯硅烷和 63 g正硅酸乙酯混合均匀, 得到混合硅烷, 备用。
[0053] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 先将
8g水和 5g浓硫酸小心缓慢键入 50g四氢呋喃中, 加热使混合物温度升至 70°C后,
滴加上述预先配好的混合硅烷, 滴加时间控制在 42min左右。 加完后, 保温反应 6小时。
[0054] 停止反应, 反应液先减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为 60°C, 真空度为 lOmmHg, 蒸馏至无液体馏出为止。 甲苯萃取 3次, 每次使用甲 苯量为 30g。 合并萃取液, 以蒸馏水洗涤 5次, 每次使用 15g蒸馏水。 洗涤结束后 , 再加入 6g无水硫酸钠干燥 5小时。 过滤除去干燥剂, 于温度为 80°C、 真空度为 0 .5mmHg条件下蒸馏得到白色的松散固体产物氟硅树脂 41.6g, 收率为 83.2%。
[0055] (3) 制备有机硅胶粘剂
[0056] 250mL三口烧瓶, 配备温度计、 分水器和回流冷凝管、 恒压加料漏斗, 油浴加 热。 依次加入 107胶 16.8g和 16g甲苯, 搅拌升温至 80°C, 加 0.18g二月桂酸二丁基 锡 (DBTL) 。 通氮气 滴加 0.13g二甲基二乙氧基硅烷溶解于 2.5g甲苯中的溶液 , 30min加完, 保温反应 3h。 然后, 加入 20g上述制备的氟硅树脂溶解于 25g甲苯 中的溶液, 升高温度至 110°C, 回流分水反应 24h。 缩聚产物加入六甲基二硅氮烷 0.12g, 异丙醇 0.46g, 保温熟化反应 5h。 反应结束后停止反应, 冷却、 出料, 得 到有机硅压敏胶粘剂。
[0057] 在容器中依次加入甲苯 200g, 有机硅压敏胶粘剂 4g和过氧化二苯甲酰 (BPO) O. lg, 搅拌均匀后, 得到的稀释胶液在聚酯薄膜上以涂胶机涂胶, 控制胶层厚度 为 0.05~0.06mm。 涂胶后在 90°C下烘干 2min, 再在 150°C下烘燥 5
min固化。 按照 GB/T 2792-1998: 压敏胶粘剂 180°剥离强度试验方法, 测得有机 硅压敏胶剥离强度为 30.5N (2.5cm) 。 按照 GB/T 17875-1999: 压敏胶粘剂加速 老化试验方法, 测得胶粘剂在 250°C下耐压缩和氧化达 72h后, 180°剥离强度为 28 ·5N (2.5cm) , 说明胶粘剂耐热性能优越。
[0058] 实施例三
[0059] ( 1) 五氟苯乙基二甲基氯硅烷合成
[0060] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 依次 加入 40g三氟甲基苯和 32g五氟苯乙烯, 搅拌溶解, 氮气保护下加入氯铂酸催化 剂 O. lg。 开启加热, 升温至 80°C后, 滴加 26g甲基二氯氢硅烷, 滴加时间控制在 1 小时左右。 淌加完后继续保温反应 1.5小时。 反应结束后, 蒸除溶剂和未反应的
甲基二氯硅烷, 减压蒸馏收集 132°C馏分 (3.75kPa) , 得五氟苯乙基二甲基氯硅 烷 46g, 气相色谱测得产物纯度为 95.8%, 收率 84.6%。
[0061] (2) 缩聚合成五氟苯基乙烯基硅树脂
[0062] 在 100mL锥形瓶中将 19.5g五氟苯乙基二甲基氯硅烷和 32g正硅酸乙酯混合均匀 , 得到混合硅烷一; 另取一 100mL锥形瓶中将 6g二甲基乙烯基一氯硅烷和 31g正 硅酸乙酯混合均匀, 得到混合硅烷二, 备用。
[0063] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 先将
10g水和 6g浓硫酸小心缓慢键入 60g四氢呋喃中, 加热使混合物温度升至 72°C后, 滴加上述预先配好的混合硅烷一, 滴加时间控制在 lh。 加完后一次缩聚反应 0.5 小时。 一次缩聚结束后, 继续滴加混合硅烷二, 滴加时间为 1小时, 滴加结束后 , 保温进行二次缩聚。
[0064] 停止反应, 反应液先减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为 60°C, 真空度为 lOmmHg, 蒸馏至无液体馏出为止。 甲苯萃取 3次, 每次使用甲 苯量为 30g。 合并萃取液, 以蒸馏水洗涤 5次, 每次使用 15g蒸馏水。 洗涤结束后 , 再加入 6g无水硫酸钠干燥 5小时。 过滤除去干燥剂, 于温度为 80°C、 真空度为 0 .5mmHg条件下蒸馏得到白色的松散固体产物五氟苯基乙烯基硅树脂 34.1g, 收率 为 68.2%。
[0065] 产物分子结构如下:
[0066]
[0067] 其中, m =2〜 8 ; n =2~4; p=2~4。
[0068] (3) 制备有机硅胶粘剂
[0069] 250mL三口烧瓶, 配备温度计、 分水器和回流冷凝管、 恒压加料漏斗, 油浴加 热。 依次加入 107胶 17.2g和 20g甲苯, 搅拌升温至 80°C, 加 0.18g二月桂酸二丁基 锡 (DBTL) 。 通氮气 滴加 0.15g二甲基二乙氧基硅烷溶解于 2.5g甲苯中的溶液 , 30min加完, 保温反应 3h。 然后, 加入 28g上述制备的氟硅树脂溶解于 25g甲苯 中的溶液, 升高温度至 110°C, 回流分水反应 24h。 缩聚产物加入六甲基二硅氮烷 O. lg, 异丙醇 0.5g, 保温熟化反应 5h。 反应结束后停止反应, 冷却、 出料, 得到
有机硅压敏胶粘剂。
[0070] 在容器中依次加入甲苯 200g, 有机硅压敏胶粘剂 4g和过氧化二苯甲酰 (BPO) O. lg, 搅拌均匀后, 得到的稀释胶液在聚酯薄膜上以涂胶机涂胶, 控制胶层厚度 为 0.05~0.06mm。 涂胶后在 90°C下烘干 2min, 再在 150°C下烘燥 5
min固化。 按照 GB/T 2792-1998: 压敏胶粘剂 180°剥离强度试验方法, 测得有机 硅压敏胶剥离强度为 29.6N (2.5cm) 。 按照 GB/T 17875-1999: 压敏胶粘剂加速 老化试验方法, 测得胶粘剂在 250°C下耐压缩和氧化达 72h后, 180°剥离强度为 28 · IN (2.5cm) 。
[0071] 实施例四
[0072] ( 1) 五氟苯乙基二甲基氯硅烷合成步骤同实施例一。
[0073] (2) 缩聚合成氟硅树脂
[0074] 在 100mL锥形瓶中将 19.5g五氟苯乙基二甲基氯硅烷和 32g正硅酸乙酯混合均匀 , 得到混合硅烷一; 在另一 100mL锥形瓶中将 10g二甲基苯基一氯硅烷和 31.5g正 硅酸乙酯混合均匀, 得到混合硅烷二; 两种混合硅烷备用。
[0075] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 先将
9g水和 6.5g浓硫酸小心缓慢键入 55g四氢呋喃中, 加热使混合物温度升至 75°C后 , 滴加上述预先配好的混合硅烷一, 滴加时间控制在 lh。 加完后一次缩聚反应 0. 5小时。 一次缩聚结束后, 继续滴加混合硅烷二, 滴加时间为 1小时, 滴加结束 后, 保温进行二次缩聚反应 5小时。
[0076] 停止反应, 反应液先减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为 60°C, 真空度为 lOmmHg, 蒸馏至无液体馏出为止。 以二甲苯萃取 3次, 每次使 用二甲苯量为 30g。 合并萃取液, 以蒸馏水洗涤 5次, 每次使用 15g蒸馏水。 洗涤 结束后, 再加入 6g无水硫酸镁干燥 5小时。 过滤除去干燥剂, 于温度为 80°C、 真 空度为 0.5mmHg条件下蒸馏得到白色的松散固体产物氟硅树脂 33.8g, 收率为 67. 6%。
[0077] 产物分子结构如下:
[0078]
[0079] 其中, m =2〜 9; n =2~4; p=2~5。
[0080] (3) 制备有机硅胶粘剂
[0081] 250mL三口烧瓶, 配备温度计、 分水器和回流冷凝管、 恒压加料漏斗, 油浴加 热。 依次加入 107胶 17.8g和 25g甲苯, 搅拌升温至 80°C, 加 0.16g二月桂酸二丁基 锡 (DBTL) 。 通氮气 滴加 0.15g二甲基二乙氧基硅烷溶解于 2.5g甲苯中的溶液 , 30min加完, 保温反应 3h。 然后, 加入 26g上述制备的氟硅树脂溶解于 25g甲苯
中的溶液, 升高温度至 110°c, 回流分水反应 24h。 缩聚产物加入六甲基二硅氮烷 O. lg, 异丙醇 0.5g, 保温熟化反应 5h。 反应结束后停止反应, 冷却、 出料, 得到 有机硅压敏胶粘剂。
[0082] 在容器中依次加入甲苯 200g, 有机硅压敏胶 4g和过氧化二苯甲酰 (BPO) O. lg , 搅拌均匀后, 得到的稀释胶液在聚酯薄膜上以涂胶机涂胶, 控制胶层厚度为 0. 05~0.06mm。 涂胶后在 90°C下烘干 2min, 再在 150°C下烘燥 5 min固化。 按照 GB/T 2792-1998: 压敏胶粘剂 180°剥离强度试验方法, 测得有机硅压敏胶剥离强度为 2 9.8N (2.5cm) 。 按照 GB/T 17875-1999: 压敏胶粘剂加速老化试验方法, 测得胶 粘剂在 250°C下耐压缩和氧化达 72h后, 180°剥离强度为 28.3N (2.5cm) 。
[0083] 实施例五
[0084] ( 1) 五氟苯乙基二甲基氯硅烷合成步骤同实施例一。
[0085] (2) 缩聚合成五氟苯基乙烯基硅树脂
[0086] 在 100mL锥形瓶中将 20g五氟苯乙基二甲基氯硅烷和 30g正硅酸乙酯混合均匀, 得到混合硅烷一; 在另一 100mL锥形瓶中将 3g二甲基乙烯基一氯硅烷和 30g正硅 酸乙酯混合均匀, 得到混合硅烷二, 备用。
[0087] 500mL三口烧瓶, 配备温度计、 回流冷凝管和恒压滴加漏斗, 油浴加热。 先将
8g水和 6g浓硫酸小心缓慢键入 50g四氢呋喃中, 加热使混合物温度升至 71°C后, 慢速滴加上述预先配好的混合硅烷一, 滴加时间控制在 lh。 加完后一次缩聚反 应 0.5小时。 一次缩聚结束后, 继续滴加混合硅烷二, 滴加时间为 1小时, 滴加结 束后, 保温进行二次缩聚反应 5小时。
[0088] 停止反应, 反应液先减压蒸馏除去副产物乙醇及溶剂四氢呋喃, 蒸馏的温度为 60°C, 真空度为 lOmmHg, 蒸馏至无液体馏出为止。 甲苯萃取 3次, 每次使用甲 苯量为 25g。 合并萃取液, 以蒸馏水洗涤 5次, 每次使用 12g蒸馏水。 洗涤结束后 , 再加入 5g无水硫酸钠干燥 5小时。 过滤除去干燥剂, 于温度为 80°C、 真空度为 0 .5mmHg条件下蒸馏得到白色的松散固体产物五氟苯基乙烯基硅树脂 35.6g, 收率 为 71.2%。
[0089] 产物分子结构如下:
[0090]
[0091] 其中, m =2〜 12; n=2~5; p=l〜 4。
[0092] (3) 制备有机硅胶粘剂
[0093] 250mL三口烧瓶, 配备温度计、 分水器和回流冷凝管、 恒压加料漏斗, 油浴加 热。 依次加入 107胶 18.1g和 25g甲苯, 搅拌升温至 80°C, 力叩 .2g二月桂酸二丁基锡 (DBTL) 。 通氮气 滴加 0.15g二甲基二乙氧基硅烷溶解于 2.8g甲苯中的溶液, 30min加完, 保温反应 3h。 然后, 加入 27g上述制备的氟硅树脂溶解于 25g甲苯中 的溶液, 升高温度至 110°C, 回流分水反应 24h。 缩聚产物加入六甲基二硅氮烷 0.
lg, 异丙醇 0.5g, 保温熟化反应 5h。 反应结束后停止反应, 冷却、 出料, 得到有 机硅压敏胶粘剂。
[0094] 在容器中依次加入甲苯 200g, 有机硅压敏胶 4g和过氧化二苯甲酰 (BPO) O. lg , 搅拌均匀后, 得到的稀释胶液在聚酯薄膜上以涂胶机涂胶, 控制胶层厚度为 0. 05~0.06mm。 涂胶后在 90°C下烘干 2min, 再在 150°C下烘燥 5 min固化。 按照 GB/T 2792-1998: 压敏胶粘剂 180°剥离强度试验方法, 测得有机硅压敏胶剥离强度为 3 0.3N (2.5cm) 。 按照 GB/T 17875-1999: 压敏胶粘剂加速老化试验方法, 测得胶 粘剂在 250°C下耐压缩和氧化达 72h后, 180°剥离强度为 29. IN (2.5cm) 。
Claims
[权利要求 1] 一种氟硅树脂, 其特征在于, 所述氟硅树脂的化学结构式为:
其中, R=甲基、 苯基、 乙烯基或氢;
m=2〜 20; n=l〜 5; p=l〜 8
[权利要求 2] 权利要求 1所述氟硅树脂的制备方法, 其特征在于, 包括如下步骤:
(1) 以五氟苯乙烯、 甲基二氯硅烷为原料, 在贵金属盐催化下, 制 备五氟苯乙基二甲基氯硅烷;
(2) 将五氟苯乙基二甲基氯硅烷与正硅酸乙酯的混合物滴加入 7JC/无 机酸 /有机溶剂的混合液中进行一次缩聚反应; 然后再滴加三烃基一 氯硅烷与正硅酸乙酯的混合物, 再次缩聚反应后, 制备氟硅树脂。
[权利要求 3] 根据权利要求 2所述氟硅树脂的制备方法, 其特征在于, 五氟苯乙烯 、 贵金属盐、 甲基二氯硅烷的质量比为 1: (0.003〜 0.006) : (0.5〜 2
) ; 五氟苯乙基二甲基氯硅烷与正硅酸乙酯的混合物中, 五氟苯乙基 二甲基氯硅烷与正硅酸乙酯的质量比为 (1〜 6) : (1〜 10) ; 三烃基 一氯硅烷与正硅酸乙酯的混合物中, 三烃基一氯硅烷与正硅酸乙酯的 质量比为 (1〜 3) : (1〜 10) 。
[权利要求 4] 根据权利要求 2所述氟硅树脂的制备方法, 其特征在于,
步骤 (1) 为, 将五氟苯乙烯溶解于芳香烃类溶剂中, 氮气保护下加 入贵金属盐催化剂; 然后于 50〜 140°C下滴加甲基二氯硅烷; 滴加完 成后保温反应 1~ 10小时, 制备五氣苯乙基二甲基氯桂焼;
步骤 (2) 为, 将水、 无机酸分散在有机溶剂中, 然后于 60〜 80°C下 滴加五氟苯乙基二甲基氯硅烷与正硅酸乙酯的混合物, 滴加完成后保 温进行一次缩聚 0.5〜 1小时; 然后再滴加三烃基一氯硅烷与正硅酸乙 酯的混合物, 滴加完成后保温进行再次缩聚反应 1〜 6小时, 制备氟硅 树脂。
[权利要求 5] 根据权利要求 4所述氟硅树脂的制备方法, 其特征在于, 所述芳香烃 类溶剂为甲苯、 二甲苯、 三氟甲苯、 1,3 -双 (三氟甲基) 苯中的一种 ; 所述贵金属盐为氯铂酸; 所述三烃基一氯硅烷为三甲基氯硅烷、 二 甲基氢基一氯硅烷、 二甲基乙烯基一氯硅烷、 苯基二甲基一氯硅烷中 的一种; 所述无机酸为浓硫酸或者浓盐酸; 所述有机溶剂为四氢呋喃
[权利要求 6] 根据权利要求 4所述氟硅树脂的制备方法, 其特征在于, 步骤 (1) 中
, 滴加甲基二氯硅烷的时间为 0.5〜 5小时; 步骤 (2) 中, 滴加三烃 基一氯硅烷与正硅酸乙酯的混合物的时间为 0.5〜 1小时。
[权利要求 7] 根据权利要求 4所述氟硅树脂的制备方法, 其特征在于, 步骤 (1) 反 应结束后, 反应液经过蒸除、 减压蒸馏得到五氟苯乙基二甲基氯硅烷 ; 步骤 (2) 再次缩聚反应结束后, 反应液经过冷却、 减压蒸馏、 分 液处理、 萃取、 蒸馏水洗涤、 干燥、 过滤、 蒸馏得到氟硅树脂。
[权利要求 8] 一种五氟苯乙基二甲基氯硅烷的制备方法, 其特征在于, 包括以下步 骤, 将五氟苯乙烯溶解于芳香烃类溶剂中, 氮气保护下加入贵金属盐 催化剂; 然后于 50〜 140°C下滴加甲基二氯硅烷; 滴加完成后保温反 应 1~10小时, 制备五氟苯乙基二甲基氯硅烷。
[权利要求 9] 根据权利要求 8所述五氟苯乙基二甲基氯硅烷的制备方法, 其特征在 于, 所述芳香烃类溶剂为甲苯、 二甲苯、 三氟甲苯、 1,3 -双 (三氟甲 基) 苯中的一种; 所述贵金属盐为氯铂酸; 滴加甲基二氯硅烷的时间 为; 反应结束后, 反应液经过蒸除、 减压蒸馏得到五氟苯乙基二甲基 氯硅焼。
[权利要求 10] 权利要求 8所述五氟苯乙基二甲基氯硅烷的制备方法制备的五氟苯乙 基二甲基氯桂焼。
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