CN118580495B - Phenyl dimethyl end-capped or triphenyl end-capped methylphenyl silicone oil and preparation method thereof - Google Patents
Phenyl dimethyl end-capped or triphenyl end-capped methylphenyl silicone oil and preparation method thereof Download PDFInfo
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- CN118580495B CN118580495B CN202411067331.7A CN202411067331A CN118580495B CN 118580495 B CN118580495 B CN 118580495B CN 202411067331 A CN202411067331 A CN 202411067331A CN 118580495 B CN118580495 B CN 118580495B
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- methylphenyl silicone
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- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical group C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000012676 equilibrium polymerization Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- -1 phosphate ester Chemical class 0.000 claims description 7
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 238000000526 short-path distillation Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims 2
- 230000006378 damage Effects 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000903 blocking effect Effects 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- YQJPWWLJDNCSCN-UHFFFAOYSA-N 1,3-diphenyltetramethyldisiloxane Chemical group C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 YQJPWWLJDNCSCN-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 229920002545 silicone oil Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GCFSZYMVQAVHPW-UHFFFAOYSA-N 2-methyl-2-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[Si]1(O[SiH2]O[SiH2]O1)c1ccccc1 GCFSZYMVQAVHPW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- OKONWUJRLPUUJT-UHFFFAOYSA-N dimethyl-phenyl-triphenylsilyloxysilane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 OKONWUJRLPUUJT-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical group O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- FDTBETCIPGWBHK-UHFFFAOYSA-N hydroxy-dimethyl-phenylsilane Chemical compound C[Si](C)(O)C1=CC=CC=C1 FDTBETCIPGWBHK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 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
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to phenyl dimethyl end-capped or triphenyl end-capped methyl phenyl silicone oil and a preparation method thereof. The methylphenyl silicone oil of the present invention comprises (i) a blocking group represented by formula (1) or formula (2), (ii) a structural unit represented by formula (3), and (iii) one or both structural units selected from the structural units represented by formula (4) and formula (5). The methylphenyl silicone oil of the invention has the advantages of high refractive index, proper viscosity, high flash point and high transparency, and also has excellent heat resistance, aging resistance and radiation resistance, and can be easily prepared by a simple and safe method.Equation (1),Equation (2),Equation (3),(4) A step of,
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to phenyl dimethyl end-capped or triphenyl end-capped methylphenyl silicone oil and a preparation method thereof.
Background
The methyl phenyl silicone oil is a silicone oil with partial methyl groups replaced by phenyl groups, and has excellent high and low temperature resistance, good lubricating performance, radiation resistance and better compatibility with materials such as plastic rubber and the like, so that the phenyl silicone oil is widely applied to the fields of lubrication, insulation, demolding, damping, vibration prevention, dust prevention and the like. There is no particular requirement for the end-capping of methylphenyl silicone oil, and currently there are mainly trimethyl end-capped methylphenyl silicone oil and methyl diphenyl end-capped methylphenyl silicone oil.
The trimethyl end capped methyl phenyl silicone oil is mainly prepared by end capped and telogenic trimethyl chlorosilane, hexamethyldisiloxane or methyl silicone oil and the like, and the pure methyl end socket has the advantages of easily obtained raw materials and relatively low price, so the market share is relatively high.
The end sealing agent of the phenyl silicone oil capped by methyl diphenyl is prepared by the processes of hydrolysis, telomerization and the like of methyl diphenyl alkoxy silane prepared by methyl alkoxy silane and chlorobenzene in the presence of metallic sodium. The methyl diphenyl terminated methyl phenyl silicone oil has the advantages of better heat resistance and is favorable for preparing methyl phenyl silicone oil with high refractive index and low viscosity.
The current method for synthesizing phenyl silicone oil mainly comprises two methods, namely an equilibrium method and a hydrolysis condensation method. The equilibrium method takes phenyl siloxane ring bodies and methyl siloxane ring bodies as raw materials and is prepared by equilibrium polymerization reaction. For example, patent document 1 discloses a method for producing a benzyl silicone oil from octamethyl cyclotetrasiloxane, methylphenyl cyclotrisiloxane, dimethyl tetraphenyl disiloxane, tetramethylammonium hydroxide, polyethylene oxide, hexamethyldisiloxane, and phthalylsulfonimide as raw materials. Patent document 2 discloses a method for producing phenyl methyl silicone oil from dimethyl diphenyl mixed cyclosiloxane, octamethyl cyclotetrasiloxane, tetramethylammonium hydroxide silicon alkoxide, and hexamethyldisiloxane.
Citation literature:
patent document 1, cn106977720a;
patent document 2, cn107759790a.
Disclosure of Invention
For trimethyl end capped methylphenyl silicone oil, the preparation requirement on a phenyl ring is relatively high, and excessive introduction of methyl can cause difficulty in obtaining silicone oil with high refractive index and low viscosity.
For methyl diphenyl end-capped phenyl silicone oil, the phenyl end-capping agent has the defects of high potential safety hazards of the preparation process and difficult purification, most of the methyl diphenyl end-capped silicone oil produced in China is used for preparing the methyl phenyl silicone oil without purification, and the phenyl end-capping agent has a high boiling point and is difficult to remove from a system, so that the performance of the methyl phenyl silicone oil is adversely affected.
The technical problem to be solved by the invention is to provide the methylphenyl silicone oil which has high refractive index, proper viscosity, high flash point, high transparency, excellent heat resistance, aging resistance and radiation resistance and can be easily prepared by a simple and safe method.
Aiming at the problems in the prior art, the invention provides phenyl dimethyl end-capped or triphenyl end-capped methylphenyl silicone oil and a preparation method thereof.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] A methylphenyl silicone oil comprising:
(i) A blocking group represented by the formula (1) or (2),
(Ii) A structural unit represented by the formula (3), and
(Iii) One or two structural units selected from the structural units shown in the formula (4) and the formula (5),
(1),(2),
(3),
(4) A step of,Formula (5).
[2] The methylphenyl silicone oil according to [1], wherein the content of the structural unit represented by formula (3) is 15 to 100 mol%, the content of the structural unit represented by formula (4) is 0 to 85 mol%, and the content of the structural unit represented by formula (5) is 0 to 45 mol%, based on the total number of moles of the structural units represented by formula (3), formula (4) and formula (5).
[3] The methylphenyl silicone oil according to [1] or [2], wherein the methylphenyl silicone oil has a structure represented by the following formula (I) or formula (II),
The compound of formula (I),
The compound of formula (II),
Wherein x, y and z represent the molar ratio of the three structural units, x+y+z=1, x is 0.15 to 1, y is 0 to 0.85, and z is 0 to 0.45.
[4] The method for preparing methylphenyl silicone oil according to any one of [1] to [3], comprising the steps of:
(a) Dehydration, namely dehydrating a mixture comprising dimethyl cyclosiloxane, phenyl cyclosiloxane, a blocking agent and a catalyst,
(B) Equilibrium polymerization by polymerizing the dehydrated mixture,
(C) Breaking the catalyst by adding an acidic neutralizing agent, and
(D) Removing low boiling point substances in the reaction system;
Wherein the phenyl cyclosiloxane is one or more selected from octaphenyl cyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, mixed ring bodies of methylphenyl and diphenyl and hydrolytic oil thereof;
The end-capping agent is diphenyl tetramethyl disiloxane or hexaphenyl disiloxane;
the catalyst is potassium hydroxide;
the acid neutralizer is at least one selected from phosphoric acid, silicon-based phosphate, acetic acid and carbon dioxide.
[5] The method according to [4], wherein the dehydration in the step (a) is performed by one of reduced pressure distillation or nitrogen bubbling or a combination of both, wherein the temperature at the time of reduced pressure distillation is 40 to 90 ℃, the relative vacuum degree is-0.08 MPa to-0.1 MPa, and the mass usage amount of the end-capping agent is 5 to 20% relative to the total mass of the dimethylcyclosiloxane and the phenylcyclosiloxane.
[6] The process according to [4], wherein in the step (b), the polymerization reaction temperature is 150 to 190℃and the amount of the catalyst to be used is 20 to 200ppm in terms of the amount of potassium based on the total weight of the reaction system.
[7] The preparation method according to [4], wherein in the step (C), the reaction system is cooled to 100-130 ℃ first, and then the acidic neutralizing agent is added to the reaction system, wherein the addition amount of the acidic neutralizing agent is 5-20 times of the catalyst by mass.
[8] The process according to [4], wherein in the step (d), the low boiling point substance in the reaction system is removed by distillation under reduced pressure or short path distillation, the pressure of distillation under reduced pressure is 100Pa or less, the temperature is 150 to 300 ℃, and the low boiling point substance is one or more selected from the group consisting of diphenyl tetramethyl disiloxane, dimethyl cyclosiloxane and methyl phenyl cyclosiloxane.
[9] The process according to [4], wherein the process further comprises a step of producing diphenyltetramethyldisiloxane or hexaphenyldisiloxane as a terminal-blocking agent,
The preparation method comprises the steps of carrying out hydrolysis reaction on phenyl dimethyl-chlorosilane in an organic solvent A in the presence of water, and then separating and purifying reaction products, wherein the separation and purification comprise layering a system after the hydrolysis reaction, and then carrying out operations of water washing, alkali neutralization, dehydration, desolventizing and reduced pressure distillation on an organic layer;
The preparation method of the hexaphenyl disiloxane comprises the steps of dissolving triphenyl silanol in an organic solvent B, then carrying out condensation reaction under the condition of solvent reflux in the presence of a base catalyst, and then separating and purifying the reaction product, wherein the separation and purification comprise cooling crystallization, filtration, water washing and drying.
[10] The production method according to [9], wherein,
The organic solvent A is a nonpolar organic solvent, and the organic solvent B is a polar organic solvent;
The alkali used for the alkali neutralization and the alkali catalyst are one or more selected from organic alkali and inorganic alkali respectively.
The phenyl dimethyl end-capped methylphenyl silicone oil can be prepared by adopting diphenyl tetramethyl disiloxane as an end-capping agent, and the problems in the preparation of the high-refractive-index and low-viscosity methylphenyl silicone oil are well solved. The diphenyl tetramethyl disiloxane has a low boiling point, which is convenient for removing low boiling point substances in the prepared methyl phenyl silicone oil so as to improve the flash point. In addition, the raw materials for preparing the diphenyl tetramethyl disiloxane can be prepared by a method such as a format method, a sodium method, a disproportionation method and the like, and the raw materials have low boiling points and are liquid, so that the raw materials can be distilled and purified, which leads to the final obtained methyl phenyl silicone oil being more excellent in heat resistance, flash point, transparency, molecular weight distribution and the like.
The triphenyl end-capped methylphenyl silicone oil can be prepared by adopting hexaphenyl disiloxane as an end-capping agent, and has the advantages of high refractive index and proper viscosity and better heat resistance, aging resistance and radiation resistance due to the large number of phenyl groups in the end-capping group. With the continuous change of market, technology and yield, the main raw materials of triphenylchlorosilane and triphenylsilanol for preparing hexaphenyl disiloxane are easy to obtain, and the price is relatively low. Hexaphenyl disiloxane, although sterically hindered, has three electron withdrawing groups, so it can polymerize with methyl ring or phenyl ring and perform equilibrium reaction under the catalysis of base. The hexaphenyl disiloxane has a relatively large tackifying coefficient for methyl phenyl silicone oil, so that the hexaphenyl disiloxane is more suitable for preparing silicone oil with medium viscosity or higher.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< Terms and definitions >
In the present specification, "methylphenyl silicone oil" means a methylphenyl silicone.
In the present specification, "room temperature" means a temperature range of 20 to 30 ℃, for example, 25 ℃.
In the present specification, the numerical range indicated by "numerical values A to B" means a range including the end point numerical values A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
< Methyl phenyl Silicone oil >
It is an object of the present invention to provide a methylphenyl silicone oil comprising:
(i) A blocking group represented by the formula (1) or (2),
(Ii) A structural unit represented by the formula (3), and
(Iii) One or two structural units selected from the structural units shown in the formula (4) and the formula (5),
(1),(2),
(3),
(4) A step of,Formula (5).
The structural units represented by the formula (1) and the formula (2) are end capping groups, which are derived from end capping agents used in the preparation process. Specifically, the phenyl dimethylsiloxane blocking group represented by formula (1) may be derived from diphenyl tetramethyldisiloxane as a blocking agent, and the triphenyl silane blocking group represented by formula (2) may be derived from hexaphenyl disiloxane blocking agent.
The structural units represented by the formulas (3), (4) and (5) are repeating units constituting a molecule chain of the methylphenyl silicone oil. The ratio of the dimethylsiloxy structural unit represented by the formula (3) to the total structural units is 15 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 85 mol%, for example 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%.
The structural units represented by the formulas (4) and (5) are structural units having phenyl groups, and the methylphenyl silicone oil of the present invention may have only any one of the structural units represented by the formulas (4) and (5), or may have both the structural units represented by the formulas (4) and (5). Wherein the proportion of the phenylmethylsiloxy structural unit represented by the formula (4) in the total structural units is 0 to 85 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%, for example 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%. The proportion of the diphenylsiloxane structural units represented by the formula (5) in the total structural units is 0 to 45 mol%, preferably 5 to 40 mol%, more preferably 10 to 35 mol%, for example 15 mol%, 20 mol%, 25 mol%, 30 mol%.
In one embodiment, the present invention provides a phenyl dimethyl-terminated methylphenyl silicone oil having the structure of formula (I) below:
The compound of formula (I),
Wherein x, y and z represent the molar ratio of the three structural units and satisfy x+y+z=1, wherein x is 0.15 to 1, preferably 0.2 to 0.9, more preferably 0.3 to 0.85, y is 0 to 0.85, preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and z is 0 to 0.45, preferably 0.05 to 0.4, more preferably 0.1 to 0.35.
For example, x may be 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, etc., y may be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, etc., and z may be 0.15, 0.2, 0.25, 0.3, etc.
The phenyl dimethyl end-capped methylphenyl silicone oil has the characteristics of high refractive index, low viscosity, high flash point, high transparency, and excellent heat resistance, ageing resistance and radiation resistance.
In another embodiment, the present invention provides a triphenyl-terminated methylphenyl silicone oil having the structure of formula (II) below:
The compound of formula (II),
Wherein x, y and z represent the molar ratio of the three structural units and satisfy x+y+z=1, wherein x is 0.15 to 1, preferably 0.2 to 0.9, more preferably 0.3 to 0.85, y is 0 to 0.85, preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and z is 0 to 0.45, preferably 0.05 to 0.4, more preferably 0.1 to 0.35.
For example, x may be 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, etc., y may be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, etc., and z may be 0.15, 0.2, 0.25, 0.3, etc.
The triphenyl-terminated methylphenyl silicone oil has the characteristics of high refractive index, medium viscosity, high flash point, high transparency, and excellent heat resistance, ageing resistance and radiation resistance.
< Preparation method >
An object of the present invention is to provide a method for producing the methylphenyl silicone oil of the present invention, characterized by comprising the steps of:
(a) Dehydration, namely dehydrating a mixture comprising dimethyl cyclosiloxane, phenyl cyclosiloxane, a blocking agent and a catalyst,
(B) Equilibrium polymerization by polymerizing the dehydrated mixture,
(C) Breaking the catalyst by adding an acidic neutralizing agent, and
(D) And (3) removing low boiling point substances in the reaction system.
In one embodiment, the preparation method of the present invention further comprises a step of preparing diphenyl tetramethyl disiloxane or hexaphenyl disiloxane as a capping agent.
The raw materials and the respective steps of the production method of the present invention are described in detail below.
Raw materials and their amounts
The dimethylcyclosiloxane used in the present invention is one or more selected from hexamethylcyclotrisiloxane (D3), octamethyltetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). From the viewpoints of easy availability of raw materials and cost-effectiveness, a dimethylsiloxane hybrid ring body is preferably used. More preferably, a mixture of octamethyl cyclotetrasiloxane (D4) and decamethyl cyclopentasiloxane (D5).
The phenylcyclosiloxane used in the present invention is one or more selected from octaphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, mixed ring bodies of methylphenyl and diphenyl groups (e.g., ring bodies having structures of both formulae (4) and (5)), and hydrolyzed oils thereof.
In one embodiment, the phenyl cyclosiloxane used is octaphenyl cyclotetrasiloxane, and the resulting methylphenyl silicone oil has the structural unit represented by formula (5) above.
In one embodiment, the phenyl cyclosiloxane used is tetramethyl tetraphenyl cyclotetrasiloxane, and the resulting methylphenyl silicone oil has the structural unit represented by formula (4) above as a repeating unit.
The end-capping agent used in the preparation method is diphenyl tetramethyl disiloxane or hexaphenyl disiloxane. In embodiments using diphenyl tetramethyl disiloxane as the endcapping agent, the resulting methylphenyl silicone oil has the endcapping group of formula (1). In embodiments using hexaphenyl disiloxane as the endcapping agent, the resulting methylphenyl silicone oil has the endcapping group of formula (2).
In the preparation method of the present invention, the suitable amount of dimethylcyclosiloxane and phenylcyclosiloxane may be selected according to the amounts of the structural units represented by the formulae (3), (4) and (5) in the product.
In one embodiment, the amount of dimethylcyclosiloxane is 15 to 100%, preferably 20 to 85% relative to the total mass of dimethylcyclosiloxane and phenylcyclosiloxane.
In one embodiment, the phenylcyclosiloxane is used in an amount of 0 to 85%, preferably 15 to 80%, relative to the total mass of dimethylcyclosiloxane and phenylcyclosiloxane.
In one embodiment, the end-capping agent is used in an amount of 5-20% relative to the total mass of the dimethylcyclosiloxane and the phenylcyclosiloxane.
The catalyst used in the invention is potassium hydroxide, which can be directly used or used in the form of alkali gel. The amount of the catalyst to be used is 20 to 200ppm, preferably 30 to 150ppm, more preferably 50 to 100ppm in terms of the amount of potassium based on the total weight of the reaction system.
Step (a) dehydration
The preparation process of the present invention first dehydrates a mixture comprising dimethylcyclosiloxane, phenylcyclosiloxane, a capping agent, and a catalyst. The purpose of dehydration is to reduce the moisture content of the system, avoid the formation of silicon hydroxyl groups, influence the quality of silicone oil, and the moisture also reduces the reactivity of the catalyst, thereby influencing the equilibrium polymerization reaction, which leads to uneven molecular weight distribution and phenyl distribution.
In one embodiment, the dehydration is performed by 1 mode or a combination of 2 modes in reduced pressure distillation or nitrogen bubbling.
Preferably, the relative vacuum degree in reduced pressure distillation is-0.08 MPa to-0.1 MPa, the reduced pressure distillation time is preferably 0.5-5 hours, preferably 1-3 hours, and the reduced pressure distillation temperature is preferably 40-90 ℃.
In one embodiment, the temperature of the reduced pressure distillation is 40 to 70 ℃, preferably 50 to 60 ℃. In another embodiment, the temperature of the reduced pressure distillation is 80 to 90 ℃, in which embodiment part of the dimethylcyclosiloxane is distilled off while dehydrating.
Preferably, the nitrogen bubbling is carried out by continuously introducing nitrogen into the mixture, preferably for a period of 0.5 to 5 hours, preferably for 1 to 3 hours, at a temperature of 20 to 40 ℃, for example, room temperature.
Step (b) Balanced polymerization
In the step (b), the dimethyl cyclosiloxane and the phenyl cyclosiloxane in the dehydrated mixture are subjected to an equilibrium polymerization reaction in the presence of a catalyst, and are subjected to a capping reaction with a capping agent, so that the methylphenyl silicone oil is obtained.
The common method for preparing the methylphenyl silicone oil is anion-catalyzed equilibrium polymerization, common catalysts are potassium hydroxide and tetramethyl ammonium hydroxide, tetramethyl ammonium hydroxide is currently used as a reaction catalyst at home, the advantage is that the reaction temperature is low, the catalyst does not remain, but the disadvantage is that the synthesized silicone oil is tasty and difficult to remove. Moreover, for preparing the triphenyl end-capped methyl phenyl silicone oil, the reaction belongs to solid-liquid polymerization reaction, and the low temperature is not beneficial to the balance of the reaction. Therefore, the invention uses potassium hydroxide as a reaction catalyst, and more preferably uses potassium hydroxide prepared into alkali gel, and can be dissolved in a system more quickly.
In one embodiment, potassium hydroxide is used in an amount of 20 to 200ppm, preferably 40 to 150ppm, more preferably 50 to 100ppm in terms of potassium, relative to the total weight of the reaction system. If the catalyst is used in too small an amount, the reaction is too slow or even not, and if the catalyst is used in too large an amount, the burden of the subsequent treatment is increased and the performance of the silicone oil is adversely affected.
In one embodiment, the polymerization temperature is 150 to 190 ℃, preferably 170 to 180 ℃, and the polymerization time is preferably 2 to 20 hours, preferably 4 to 16 hours, more preferably 6 to 18 hours.
Step (c) breaking the catalyst
After the polymerization reaction is completed, an acidic neutralizing agent is added to the reaction system to break the activity of the catalyst.
In one embodiment, the acidic neutralizing agent is at least one selected from phosphoric acid, silicon-based phosphate, acetic acid, carbon dioxide, preferably silicon-based phosphate.
In embodiments using carbon dioxide, carbon dioxide gas may be bubbled through the reaction system to neutralize the carbon dioxide with potassium hydroxide and destroy the activity of the catalyst.
In embodiments using a silicon-based phosphate, the silicon-based phosphate may be dissolved in a dimethylcyclosiloxane (e.g., octamethyl cyclotetrasiloxane) and then added to the reaction system. The mass concentration of the silicon-based phosphate dissolved in the dimethylcyclosiloxane is 3-15 mass%.
In one embodiment, the addition amount of the acid neutralizer is 5-20 times of the catalyst by mass.
In one embodiment, the temperature of the reaction system after the polymerization reaction is reduced to 100-130 ℃ first, and then the acid neutralizer is added into the reaction system.
Step (d) removing the low level
After the activity of the catalyst is broken, the low boiling point substances in the reaction system are removed.
Wherein the low boiling point substance is one or more selected from diphenyl tetramethyl disiloxane, dimethyl cyclosiloxane and methyl phenyl cyclosiloxane.
In one embodiment, the low boiling point substances in the reaction system are removed by subjecting the reaction system to reduced pressure distillation or short path distillation (molecular distillation).
Preferably, the pressure of the reduced pressure distillation is 100Pa or less.
Preferably, the temperature of the step of removing the low temperature is 300 ℃ or less, preferably 280 ℃ or less, for example 150 to 300 ℃, preferably 200 to 280 ℃. By controlling the temperature at which the silicone oil is removed within the above range, the obtained methylphenyl silicone oil is odorless and colorless, and thus has a wider range of uses.
Preparation of end-capping agent
In one embodiment, prior to step (a), a step of preparing a capping agent is also included.
Preparation of diphenyl tetramethyl disiloxane
In the invention, the preparation of diphenyl tetramethyl disiloxane comprises the steps of carrying out hydrolysis reaction of phenyl dimethyl-chlorosilane in an organic solvent A in the presence of water, and then carrying out separation and purification on a reaction product, wherein the separation and purification comprise layering a system after the hydrolysis reaction, and then carrying out operations of washing, alkali neutralization, dehydration, desolventizing and reduced pressure distillation on an organic layer.
Specifically, the organic solvent a is a nonpolar organic solvent, preferably one or more selected from benzene, toluene, xylene, n-hexane, and cyclohexane, more preferably benzene, toluene, and xylene, and most preferably toluene. The purpose of the hydrolysis reaction of phenyl dimethyl chlorosilane in a nonpolar organic solvent is to enable phenyl dimethyl silanol and diphenyl tetramethyl disiloxane produced by the hydrolysis to be dissolved in the solvent, so as to facilitate delamination with the produced hydrochloric acid and subsequent water washing neutralization.
Specifically, the temperature of the hydrolysis reaction is 20 to 80 ℃, more preferably 40 to 60 ℃.
Specifically, after the hydrolysis reaction is completed, the organic layer is washed with deionized water until ph=6 to 7.
Specifically, the organic layer is neutralized with a base after washing to ph=7 to 14, preferably ph=8 to 9. The alkali used for the alkali neutralization is one or more selected from organic alkali and inorganic alkali, wherein the organic alkali is preferably tetramethyl ammonium hydroxide, and the inorganic alkali is preferably sodium hydroxide and potassium hydroxide.
Preferably, after the neutralization with a base, the reaction system is heated to reflux of the solvent, and the condensation reaction is carried out in the presence of a base to remove the silicon hydroxyl group, and the reaction time is preferably 2 to 4 hours, and the produced water can be carried out while refluxing.
Specifically, the solvent is removed by distillation under normal pressure or reduced pressure, more preferably, distillation is performed under normal pressure to remove a part of the solvent, and then distillation is performed under reduced pressure to remove the remaining solvent. This combination allows for better solvent removal.
Preferably, after the solvent is removed, the product diphenyltetramethyldisiloxane is distilled off from the system by distillation under reduced pressure, thereby purifying the product.
Preparation of hexaphenyl disiloxane
In the invention, the preparation method of the hexaphenyl disiloxane comprises the steps of dissolving triphenyl silanol in an organic solvent B, then carrying out condensation reaction under the condition of solvent reflux in the presence of a base catalyst, and then separating and purifying the reaction product, wherein the separation and purification comprises cooling crystallization, filtration, water washing and drying.
Specifically, the organic solvent B is a polar organic solvent, preferably one or more selected from methanol, ethanol, acetone, butanone, methyl isobutyl ketone, and more preferably acetone. Since the triphenylsilanol solid is crystallized to be easily dissolved in a polar organic solvent, a polar organic solvent is used. In addition, in view of higher solubility of triphenyl silanol in ketone, it is more preferable to use acetone as a reaction solvent.
Specifically, the base catalyst is one or more selected from organic base and inorganic base, wherein the organic base is preferably tetramethyl ammonium hydroxide, and the inorganic base is preferably sodium hydroxide and potassium hydroxide.
Specifically, the reaction temperature is a solvent reflux temperature, which is advantageous for the condensation reaction to proceed.
Since triphenylsilanol is relatively sterically hindered, it is preferable to control the reflux time (reaction time) to 6 hours or more in order to obtain a higher yield of hexaphenyldisiloxane.
In the case of using acetone, since hexaphenyl disiloxane has a low solubility in acetone, after the reaction is completed, the product can be separated and purified by cooling crystallization, filtration, water washing and drying to obtain white crystals with a melting point of more than 220 ℃.
The invention also correspondingly relates to the methylphenyl silicone oil prepared by the method.
< Properties of methyl phenyl Silicone oil >
The refractive index of the methylphenyl silicone oil of the present invention is 1.49 or more, preferably 1.5 or more.
The viscosity of the methylphenyl silicone oil is 100-1200 mm < 2 >/s. More specifically, the viscosity of the phenyl dimethyl end capped methylphenyl silicone oil is 100-200 mm < 2 >/s, more preferably 100-150 mm < 2 >/s, and the viscosity of the triphenyl end capped methylphenyl silicone oil is 400-1200 mm < 2 >/s, preferably 500-1000 mm < 2 >/s.
The flash point of the methylphenyl silicone oil of the present invention is 300 ℃ or more, preferably 310 ℃ or more. More specifically, the phenyl dimethyl-terminated methylphenyl silicone oil of the present invention has a viscosity of 300 ℃ or more, preferably 310 ℃ or more, and the triphenyl-terminated methylphenyl silicone oil of the present invention has a viscosity of 340 ℃ or more, preferably 350 ℃ or more.
Examples
The invention is further illustrated by the following examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
The dimethylcyclosiloxanes used in the examples below were DMC mixtures, the main components of the composition are octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane, and the composition mainly contains octamethyl cyclotetrasiloxane.
Preparation example 1 preparation of diphenyl tetramethyl disiloxane
170.7 G of phenyl dimethyl chlorosilane (purity is more than 99%) and 256 g of toluene are placed in a dropping funnel, 207 g of deionized water is added into a four-mouth flask, the temperature is raised to 30 ℃, materials in the dropping funnel are slowly dropped into the four-mouth flask, the temperature is controlled to be about 50 ℃, after the dropping is completed, stirring is carried out for 30 minutes, a hydrochloric acid layer is removed, an organic layer is washed to be nearly neutral by deionized water, then sodium hydroxide is added to adjust the pH to be 8, the temperature is raised to the reflux of toluene, and moisture is removed until no moisture is generated any more. Then, part of toluene was distilled off at normal pressure, and finally, the temperature was not more than 150℃to distill off residual toluene. The flask contents were simply distilled to give 132 g of a colorless transparent liquid having a refractive index of 1.52 and a purity of 99.54% as measured by gas chromatography.
Preparation example 2 preparation of hexaphenyl disiloxane
200 G of triphenyl silanol, 320 g of acetone and 0.2 g of sodium hydroxide are placed in a four-necked flask, the temperature is raised to reflux and kept for 10 hours, and then the hexaphenyl disiloxane is obtained through cooling, filtering, washing and drying. The melting point was 225 ℃.
Example 1
207.2 G of dimethyl cyclosiloxane (DMC), 51.6 g of diphenyl tetramethyl disiloxane, 237.6 g of octaphenyl cyclosiloxane and 0.5 g of potassium hydroxide alkali gel catalyst with the mass concentration of 5wt% are added into a four-neck flask, the temperature is slowly increased to 50-60 ℃, the vacuum is regulated to minus 0.09MPa, and the dehydration time is 2 hours. Then heating to 170-180 ℃ for polymerization reaction, cooling to 120 ℃ after the polymerization is balanced for 6 hours, dissolving 0.3 g of trimethylsilyl phosphate in 5 g of octamethyl cyclotetrasiloxane, and adding into a flask. After stirring for 1 hour, vacuumizing until the pressure reaches below 100Pa, and heating to 280 ℃ to remove the liquid until no effluent exists. Then cooling and filtering to obtain colorless and transparent phenyl dimethyl end capped methyl phenyl silicone oil with the viscosity of 142mm2/s, the refractive index of 1.4956 and the flash point of 318 ℃.
Example 2
118.4 G of dimethyl cyclosiloxane, 44.4 g of diphenyl tetramethyl disiloxane, 272 g of tetramethyl tetraphenyl cyclotetrasiloxane and 0.5 g of potassium hydroxide alkali gel catalyst with the mass concentration of 5% are added into a four-neck flask, the temperature is slowly increased to 50-60 ℃, the vacuum is regulated to minus 0.09MPa, and the dehydration time is 2 hours. Then heating to 170-180 ℃ for polymerization reaction, cooling to 120 ℃ after the polymerization is balanced for 6 hours, dissolving 0.3 g of trimethylsilyl phosphate in 5g of octamethyl cyclotetrasiloxane, and adding into a four-necked flask. After stirring for 1 hour, vacuumizing until the pressure reaches below 100Pa, and heating to 280 ℃ to remove the liquid until no effluent exists. Cooling and filtering to obtain colorless transparent phenyl dimethyl end capped methyl phenyl silicone oil with viscosity of 125mm2/s, refraction of 1.51 and flash point of 325 deg.c.
Example 3
571.4 G of dimethyl cyclosiloxane, 143 g of hexaphenyl disiloxane, 285.6 g of octaphenyl cyclotetrasiloxane and 2g of potassium hydroxide alkali gel catalyst with mass concentration of 5% are added into a four-neck flask, the temperature is slowly increased to 50-60 ℃, vacuum is regulated to minus 0.09MPa, and dehydration time is 2 hours. Then heating to 170-180 ℃ for polymerization reaction, cooling to 120 ℃ after the polymerization is balanced for 12 hours, dissolving 1.2 g of trimethylsilyl phosphate in 10 g of octamethyl cyclotetrasiloxane, and adding into a four-necked flask. After stirring for 1 hour, vacuumizing to below 100Pa, and heating to 280 ℃ to remove low pressure until no effluent exists. Cooling and filtering to obtain colorless transparent triphenyl end capped methyl phenyl silicone oil with viscosity of 500 mm2/s, refraction of 1.494 and flash point of 342 deg.c.
Example 4
529.4 G of dimethyl cyclosiloxane, 117.7 g of hexaphenyl disiloxane, 352.9 g of octaphenyl cyclotetrasiloxane and 2g of potassium hydroxide alkali gel catalyst with mass concentration of 5% are added into a four-neck flask, the temperature is slowly increased to 50-60 ℃, vacuum is regulated to-0.09 MPa, and dehydration is carried out for 2 hours. Then heating to 170-180 ℃ for polymerization reaction, cooling to 120 ℃ after the polymerization is balanced for 12 hours, dissolving 1.2 g of trimethylsilyl phosphate in 10g of octamethyl cyclotetrasiloxane, and adding into a four-necked flask. After stirring for 1 hour, vacuumizing until the pressure reaches below 100Pa, and heating to 280 ℃ to remove the liquid until no effluent exists. Cooling and filtering to obtain colorless transparent triphenyl terminated methyl phenyl silicone oil with the viscosity of 990mm2/s, the refraction of 1.5026 and the flash point of 356 ℃.
Industrial applicability
The methylphenyl silicone oil can be widely applied to the fields of lubrication, insulation, demolding, damping, vibration prevention, dust prevention and the like.
Claims (8)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496561A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of equally distributed methyl phenyl silicone rubber preparation method of phenyl |
| CN115386088A (en) * | 2022-10-12 | 2022-11-25 | 中国科学院兰州化学物理研究所 | Fluorine-containing silicone oil and preparation method and application thereof |
| CN117777447A (en) * | 2023-12-29 | 2024-03-29 | 江西蓝星星火有机硅有限公司 | Method for preparing methylphenyl silicone oil by one-pot process |
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| JPH0641309A (en) * | 1992-07-21 | 1994-02-15 | Toray Dow Corning Silicone Co Ltd | Production of diorganosiloxane diorganosilazane copolymer |
| CN103709407B (en) * | 2013-11-29 | 2016-03-09 | 山东东岳有机硅材料有限公司 | A kind of preparation method of phenyl silicone oil |
| RU2643367C1 (en) * | 2017-05-11 | 2018-02-01 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method for producing methyl (phenyl) siloxane oligomers with terminal triphenyl-silyl groups |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496561A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of equally distributed methyl phenyl silicone rubber preparation method of phenyl |
| CN115386088A (en) * | 2022-10-12 | 2022-11-25 | 中国科学院兰州化学物理研究所 | Fluorine-containing silicone oil and preparation method and application thereof |
| CN117777447A (en) * | 2023-12-29 | 2024-03-29 | 江西蓝星星火有机硅有限公司 | Method for preparing methylphenyl silicone oil by one-pot process |
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