CN109608639A - A kind of organopolysiloxane catalyst and its preparation method and application - Google Patents
A kind of organopolysiloxane catalyst and its preparation method and application Download PDFInfo
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- CN109608639A CN109608639A CN201811455759.3A CN201811455759A CN109608639A CN 109608639 A CN109608639 A CN 109608639A CN 201811455759 A CN201811455759 A CN 201811455759A CN 109608639 A CN109608639 A CN 109608639A
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- hydroxide
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- alkali
- organopolysiloxane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002585 base Substances 0.000 claims abstract description 27
- BIFQHCGLXZWNLN-UHFFFAOYSA-N 2,2,6-trifluoro-4-methyl-4-propyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCC[Si]1(C)O[SiH](F)O[Si](F)(F)O1 BIFQHCGLXZWNLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 12
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 88
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 86
- -1 trifluoro propyl methyl Chemical group 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 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
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 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 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 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 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UXRVNHHPRRDXJG-UHFFFAOYSA-M phosphane tetrabutylazanium hydroxide Chemical compound P.[OH-].C(CCC)[N+](CCCC)(CCCC)CCCC UXRVNHHPRRDXJG-UHFFFAOYSA-M 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- OBBQDLHBLQTARQ-UHFFFAOYSA-N hexan-1-amine;hydrate Chemical compound [OH-].CCCCCC[NH3+] OBBQDLHBLQTARQ-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- HJLARPLSJYOZTN-UHFFFAOYSA-N O1[SiH](C=2C=CC=CC=2)O[SiH](C=2C=CC=CC=2)O[SiH](C=2C=CC=CC=2)O[SiH]1C1=CC=CC=C1 Chemical compound O1[SiH](C=2C=CC=CC=2)O[SiH](C=2C=CC=CC=2)O[SiH](C=2C=CC=CC=2)O[SiH]1C1=CC=CC=C1 HJLARPLSJYOZTN-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 102000031635 methyl-CpG binding proteins Human genes 0.000 abstract 1
- 108091009877 methyl-CpG binding proteins Proteins 0.000 abstract 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 14
- 230000006837 decompression Effects 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 14
- 239000004519 grease Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 229920002545 silicone oil Polymers 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005573 silicon-containing polymer Polymers 0.000 description 5
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IHRMXHHFNOEOEA-UHFFFAOYSA-N 2-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C1(=CC=CC=C1)[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 IHRMXHHFNOEOEA-UHFFFAOYSA-N 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SDPBQTFSSSPDBS-UHFFFAOYSA-N pentan-1-amine;hydrate Chemical compound [OH-].CCCCC[NH3+] SDPBQTFSSSPDBS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical group CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of organopolysiloxane catalyst and its preparation method and application, the organopolysiloxane catalyst is the trifluoro propyl Methyl-CpG binding proteins of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali.The preparation method of the organopolysiloxane catalyst includes: that alkali metal hydroxide or quaternary ammonium base or season phosphine alkali react at 50-160 DEG C with trifluoro propyl methyl cyclotrisiloxane, utilize the water in solvent azeotropic distillation removing system, then again solvent removed by vacuum and it is low wave object, obtain catalyst product；The catalyst can be used for the ring-opening polymerization of cyclosiloxane.Organopolysiloxane catalyst provided by the invention, not hygroscopic, the low within easy reach of viscosity.Hydroxy radical content using organopolysiloxane made from the catalyst is low, and performance is stablized.The catalyst has good industrial applications prospect.
Description
Technical field
It catalyst of homopolymerization or combined polymerization that the present invention relates to a kind of for being catalyzed cyclosiloxane and preparation method thereof and answers
With.
Background technique
Organopolysiloxane is that occur in organo-silicon compound earliest, most species, the most comprehensive a kind of organosilicon of research
Polymer.Its skeleton main chain is constituted with alternate silicon, oxygen atom and is connected to organic group (R) on silicon atom, and structural formula is
(RnSiO4-n/2)m.Organopolysiloxane makes it have a variety of excellent physics, chemical property, such as due to its special structure
High-low temperature resistant, weatherability, oxidative resistance, release property, hydrophobicity and physiological inertia etc. are first and are industrially applied
Element polymer occupies indispensable status in high molecular material.
Currently, there are mainly two types of the synthetic methods of organopolysiloxane: ring-opening polymerization and polycondensation reaction.Ring-opening polymerisation
Reaction is exactly to polymerize cyclosiloxane to form linear organopolysiloxane using catalyst.Polycondensation reaction can be divided into again Hydrolyze method and
Non-aqueous solution, Hydrolyze method are exactly that the organosilan of functionalized silicon base is obtained polysiloxanes by hydrolytic condensation, and non-aqueous solution is benefit
Form silicon oxygen silicon key with the mutual condensation between function radical silicide or silicon-carbon bonds obtain polysiloxanes (Feng Shengyu etc., it is " organic
Polymeric silicon and its application ", Chemical Industry Press, 2004:9-24).
The catalyst of ring-opening polymerisation has two kinds of alkalinity and acidity.Basic catalyst mainly has alkali metal hydroxide, alkali gold
Belong to alkoxide, silicon alkoxide, quaternary ammonium base, season phosphine alkali, silanol quaternary ammonium base, silanol season phosphine alkali etc..Wherein, industrially more the most commonly used is four
Ammonium hydroxide, potassium hydroxide or their poly dimethyl silicon alkoxide.
The silicon alkoxide of tetramethylammonium hydroxide or potassium hydroxide needs to completely cut off air preservation, they are easy to absorb in air
Moisture, these moisture can serve as end-capping reagent in polymerization reaction, silicone hydroxyl is introduced into polymer, so that polymer end base junction
Structure is difficult to control, and finally influences properties of product.
Summary of the invention
The purpose of the present invention is to provide a kind of not hygroscopic organopolysiloxane catalyst and preparation method thereof and answer
With.
Organopolysiloxane catalyst of the present invention is the trifluoro of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali
Hydroxypropyl methyl silicon alkoxide, its structure are shown below:
Wherein n=3-10, M are the cation of potassium, rubidium, caesium, quaternary ammonium base, season phosphine alkali.
Invention further provides the preparation methods of above-mentioned organopolysiloxane catalyst, comprising: alkali metal hydroxide
Object or quaternary ammonium base or season phosphine alkali and trifluoro propyl methyl cyclotrisiloxane are at 50-160 DEG C, in water and organic at preferably 70-140 DEG C
Reacted in the presence of solvent, using the water in solvent azeotropic distillation removing system, then again solvent removed by vacuum and it is low wave object, obtain
Catalyst product.The value of n can be controlled according to the ratio of alkali and trifluoro propyl methyl cyclotrisiloxane.Generally, product
In n be an average value, that is, product is the mixture of different n values.The amount of water usually makes alkali metal hydroxide
The concentration of object or quaternary ammonium base or season phosphine alkali in aqueous solution is 10-65wt%, preferably 30-60wt%.
The catalyst can be used for the ring-opening polymerization of cyclosiloxane, to prepare line style organopolysiloxane；Organic poly- silicon
The structure of oxygen alkane is shown below,
Wherein, p=50-10000, q/p=0-0.5, m/ (p+q)=0-0.1, p+q+m=50-10000, R1 be methyl or
Phenyl, R2 are methyl or phenyl.
In another embodiment, the preparation method of organopolysiloxane catalyst of the present invention includes following step
It is rapid:
1) trifluoro propyl methyl cyclotrisiloxane and the aqueous solution of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali are mixed
It is combined, organic solvent is added, is reacted at 50-160 DEG C, the water of raw material and reaction generation is removed using water segregator, until
Anhydrous generation；
2) solvent removed by vacuum is down to room temperature under nitrogen protection, and product is poured into closed preservation in container.Wherein, have
The value of n in machine polysiloxane catalysts product general formula can be carried out by the ratio of alkali and trifluoro propyl methyl cyclotrisiloxane
Control.
It is preferred that alkali metal hydroxide is hydrogen-oxygen in the preparation method of organopolysiloxane catalyst of the present invention
Change one of potassium, rubidium hydroxide, cesium hydroxide or a variety of.
Further, the preferred potassium hydroxide of alkali metal hydroxide.
It is preferred that quaternary ammonium base is tetramethyl hydroxide in the preparation method of organopolysiloxane catalyst of the present invention
Ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, four hexyl ammonium hydroxide
One of or it is a variety of.
Further, the preferred tetramethylammonium hydroxide of quaternary ammonium base.
It is preferred that season phosphine alkali is tetrabutylammonium hydroxide in the preparation method of organopolysiloxane catalyst of the present invention
Phosphine.
The dosage of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali is the 6- of trifluoro propyl methyl cyclotrisiloxane quality
50wt%.When alkali metal hydroxide, preferably 6-25wt%；When quaternary ammonium base, preferably 11-40wt%；It is excellent when this season phosphine alkali
Select 34-50wt%.
In the preparation method of organopolysiloxane catalyst of the present invention, organic solvent be benzene,toluene,xylene,
One of n-hexane, hexamethylene, chlorobenzene, fluorobenzene, carbon tetrachloride, chloroform, dichloroethanes, ethyl acetate, acetonitrile are a variety of.
The additive amount of organic solvent is usually the 50-200wt% of trifluoro propyl methyl cyclotrisiloxane, preferably 80-120wt%.
Further, one of the preferred benzene,toluene,xylene of organic solvent, n-hexane, hexamethylene or a variety of.
Further, when using potassium hydroxide, one of the preferred benzene,toluene,xylene of solvent, n-hexane, hexamethylene
Or it is a variety of.
Further, when using tetramethylammonium hydroxide, the preferred toluene of solvent.
Further, when using tetrabutylammonium hydroxide phosphine, the preferred dimethylbenzene of solvent.
In the preparation method of organopolysiloxane catalyst of the present invention, reaction temperature is 50-160 DEG C.
Further, preferred 90-160 DEG C of reaction temperature.
Organopolysiloxane catalyst of the present invention can be used for being catalyzed the ring-opening polymerization of cyclosiloxane, to make
Standby line style organopolysiloxane, the dosage of catalyst are 0.01-1wt%, and polymeric reaction temperature is 90-180 DEG C.
Invention further provides the ring-opening polymerisations that the organopolysiloxane catalyst is used to be catalyzed cyclosiloxane
The purposes of reaction.Further, cyclosiloxane includes hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl ring five
Siloxanes, trimethyl trivinyl cyclotrisiloxane, t etram-ethyltetravinylcyclotetrasiloxane, four silicon oxygen of tetramethyl tetraphenyl ring
One of alkane, octaphenylcyclotetrasiloxane are a variety of.
Further, the preferred octamethylcy-clotetrasiloxane of cyclosiloxane, t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl four
Phenyl cyclotetrasiloxane, octamethylcy-clotetrasiloxane.
Organopolysiloxane catalyst of the present invention is used to be catalyzed the ring-opening polymerization of cyclosiloxane, wherein urges
The dosage of agent is the 0.01-1wt% of monomer gross mass.
Further, the preferred 0.01-0.1wt% of catalyst amount.
Organopolysiloxane catalyst of the present invention is used to be catalyzed the ring-opening polymerization of cyclosiloxane, wherein poly-
Closing reaction temperature is 90-180 DEG C.
Wherein, when catalyst is potassium hydroxide silicon alkoxide, preferred 140-180 DEG C of reaction temperature.
Further, preferred 155-165 DEG C of reaction temperature.
Wherein, when catalyst is tetramethylammonium hydroxide silicon alkoxide, preferred 90-110 DEG C of reaction temperature.
Further, preferred 95-105 DEG C of reaction temperature.
Wherein, when catalyst is tetra-n-butyl phosphonium hydroxide silicon alkoxide, preferred 120-140 DEG C of reaction temperature.
Further, preferred 125-135 DEG C of reaction temperature.
The ring-opening polymerization of organopolysiloxane catalyst cyclosiloxane of the present invention has to prepare line style
Machine polysiloxanes, wherein the structural formula of organopolysiloxane is shown below:
Wherein, p=50-10000, q/p=0-0.5, m/ (p+q)=0-0.1, p+q+m=50-10000, R1 be methyl or
Phenyl, R2 are methyl or phenyl.
In the ring-opening polymerization, end-capping reagent can be used, end-capping reagent is that can provide usual chemical group, such asEqual compounds.
Advantages of the present invention
Organopolysiloxane catalyst provided by the invention, not hygroscopic, the low within easy reach of viscosity.Use the catalyst system
The hydroxy radical content of the organopolysiloxane obtained is low, and performance is stablized.The catalyst has good industrial applications prospect.
Specific embodiment
Embodiment 1
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 84g, benzene 60ml are warming up to reflux, solid under stirring
Gradually dissolution forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 8.29g water, then isothermal reaction
1h, then remaining benzene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent grease.
Catalyst obtains base number by acid base titration, so as to converse n value, is specifically shown in Table 1.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, is dehydrated 1h under 50 DEG C, 10mbar, and then using the broken sky of nitrogen, decamethyl tetrasiloxane 41.99g is added, on
Catalyst 0.13g is stated, 165 DEG C of polymerization reaction 3h are warming up to, silicon substrate phosphate 1.96g catalyst neutralisation, stirring is then added
After 0.5h, removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colorless and transparent silicone oil.
Embodiment 2
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 84g, toluene 60ml are warming up to reflux under stirring, Gu
Body, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, and after collecting 8.29g water, then constant temperature is anti-
1h is answered, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent oil
Shape object.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added decamethyl tetrasiloxane 41.99g, and above-mentioned catalyst 0.13g is warming up to 165 DEG C of polymerization reaction 3h, silicon is then added
Base phosphate 1.96g catalyst neutralisation, stir 0.5h after, removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colorless and transparent
Silicone oil.
Embodiment 3
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 84g, dimethylbenzene 60ml are warming up to reflux under stirring,
Solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 8.29g water, then constant temperature
1h is reacted, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent
Grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, is dehydrated 1h under 50 DEG C, 10mbar, and then using the broken sky of nitrogen, it is poly- that the end-vinyl that molecular weight is 500 is added
Dimethylsiloxane oligomer 67.57g, above-mentioned catalyst 0.13g are warming up to 165 DEG C of polymerization reaction 3h, and silicon substrate phosphorus is then added
Acid esters 1.96g catalyst neutralisation, stir 0.5h after, removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colorless and transparent silicon
Oil.
Embodiment 4
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 84g, n-hexane 60ml are warming up to reflux under stirring,
Solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 8.29g water, then constant temperature
1h is reacted, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent
Grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added the end-vinyl dimethyl silicone polymer oligomer 67.57g that molecular weight is 500, and above-mentioned catalyst 0.13g is warming up to
Then silicon substrate phosphate 1.96g catalyst neutralisation is added in 165 DEG C of polymerization reaction 3h, after stirring 0.5h, under 180 DEG C, 10mbar
Remove it is low wave object 2h, obtain colorless and transparent silicone oil.
Embodiment 5
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 84g, hexamethylene 60ml are warming up to reflux under stirring,
Solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 8.29g water, then constant temperature
1h is reacted, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent
Grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 1.74g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added the end-vinyl dimethyl silicone polymer oligomer 0.71g that molecular weight is 500, and above-mentioned catalyst 0.13g is warming up to
Then silicon substrate phosphate 1.96g catalyst neutralisation is added in 165 DEG C of polymerization reaction 3h, after stirring 0.5h, under 180 DEG C, 10mbar
Remove it is low wave object 2h, obtain colorless and transparent raw rubber.
Embodiment 6
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 112g, toluene 60ml are warming up to reflux under stirring, Gu
Body, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, and after collecting 8.29g water, then constant temperature is anti-
1h is answered, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent oil
Shape object.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 1.74g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added the end-vinyl dimethyl silicone polymer oligomer 0.71g that molecular weight is 500, and above-mentioned catalyst 0.17g is warming up to
Then silicon substrate phosphate 1.96g catalyst neutralisation is added in 165 DEG C of polymerization reaction 3h, after stirring 0.5h, under 180 DEG C, 10mbar
Remove it is low wave object 2h, obtain colorless and transparent raw rubber.
Embodiment 7
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Aqueous solutions of potassium (60wt%) 16.7g, trifluoro propyl methyl cyclotrisiloxane 139g, toluene 60ml are warming up to reflux under stirring, Gu
Body, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, and after collecting 8.29g water, then constant temperature is anti-
1h is answered, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent oil
Shape object.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 274g, t etram-ethyltetravinylcyclotetrasiloxane 0.96g, octaphenylcyclotetrasiloxane 726 take off under 50 DEG C, 10mbar
Water 1h, then using the broken sky of nitrogen, the end-vinyl dimethyl silicone polymer oligomer 1.51g for being added that molecular weight is 500 is above-mentioned
Catalyst 0.22g is warming up to 165 DEG C of polymerization reactions for 24 hours, and silicon substrate phosphate 1.96g catalyst neutralisation is then added, and stirs 0.5h
Afterwards, it is cooled to room temperature, obtains the crude product of viscoelasticity.It is dissolved using the toluene of 10000mL, then with the methanol of 10000mL
It is precipitated, pours out supernatant liquor, lower sediment is cleaned using methanol, repeats above-mentioned dissolution and precipitating 2 times.Then by sediment
Drying for 24 hours, obtains colorless and transparent raw rubber at 120 DEG C, 10mbar.
Embodiment 8
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added tetramethyl
Ammonium hydroxide aqueous solution (50wt%) 50g, trifluoro propyl methyl cyclotrisiloxane 129g, toluene 200ml are warming up to back under stirring
Stream, solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 27.31g water, then
Isothermal reaction 1h, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colourless
Bright grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, is dehydrated 1h under 50 DEG C, 10mbar, and then using the broken sky of nitrogen, decamethyl tetrasiloxane 20.99g is added, on
State catalyst 0.12g, be warming up to 110 DEG C of polymerization reaction 3h, then heat to 150 DEG C of destruction catalyst, continue 0.5h, finally in
180 DEG C, remove under 10mbar it is low wave object 2h, obtain colorless and transparent silicone oil.
Embodiment 9
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added tetramethyl
Ammonium hydroxide aqueous solution (50wt%) 50g, trifluoro propyl methyl cyclotrisiloxane 172g, toluene 200ml are warming up to back under stirring
Stream, solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 27.31g water, then
Isothermal reaction 1h, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colourless
Bright grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added divinyl tetramethyl disiloxane 12.59g, and above-mentioned catalyst 0.16g is warming up to 110 DEG C of polymerization reaction 3h, so
After be warming up to 150 DEG C of destruction catalyst, continue 0.5h, finally removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colourless
Bright silicone oil.
Embodiment 10
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added tetramethyl
Ammonium hydroxide aqueous solution (50wt%) 50g, trifluoro propyl methyl cyclotrisiloxane 215g, toluene 200ml are warming up to back under stirring
Stream, solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 27.31g water, then
Isothermal reaction 1h, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colourless
Bright grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added divinyl tetramethyl disiloxane 6.30g, and above-mentioned catalyst 0.19g is warming up to 110 DEG C of polymerization reaction 3h, then
Be warming up to 150 DEG C of destruction catalyst, continue 0.5h, finally removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colorless and transparent
Silicone oil.
Embodiment 11
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added four positive fourths
Base phosphonium hydroxide aqueous solution (40wt%) 150g, trifluoro propyl methyl cyclotrisiloxane 136g, toluene 500ml stir lower heating
To reflux, solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, when collection 91.96g water
Afterwards, then isothermal reaction 1h, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains nothing
The transparent grease of color.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added decamethyl tetrasiloxane 10.50g, and above-mentioned catalyst 0.16g is warming up to 130 DEG C of polymerization reaction 3h, then heats to
180 DEG C of destruction catalyst continue 0.5h.Finally removed under 180 DEG C, 10mbar it is low wave object 2h, obtain colorless and transparent silicone oil.
Embodiment 12
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added four positive fourths
Base phosphonium hydroxide aqueous solution (40wt%) 150g, trifluoro propyl methyl cyclotrisiloxane 169g, toluene 500ml stir lower heating
To reflux, solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, when collection 91.96g water
Afterwards, then isothermal reaction 1h, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains nothing
The transparent grease of color.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, t etram-ethyltetravinylcyclotetrasiloxane 11.62g are dehydrated 1h under 50 DEG C, 10mbar, then broken using nitrogen
Sky, is added the end-vinyl dimethyl silicone polymer oligomer 8.45g that molecular weight is 500, and above-mentioned catalyst 0.19g is warming up to
130 DEG C of polymerization reaction 3h then heat to 180 DEG C of destruction catalyst, continue 0.5h.It is finally removed under 180 DEG C, 10mbar low
Object 2h is waved, colorless and transparent silicone oil is obtained.
Comparative example 1
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Lithium aqueous solution (60wt%) 4.11g, trifluoro propyl methyl cyclotrisiloxane 84g, dimethylbenzene 60ml are warming up to reflux under stirring,
Solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 2.04g water, then constant temperature
1h is reacted, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent
Grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, is dehydrated 1h under 50 DEG C, 10mbar, and then using the broken sky of nitrogen, it is poly- that the end-vinyl that molecular weight is 500 is added
Dimethylsiloxane oligomer 67.57g, above-mentioned catalyst 0.13g, are warming up to 165 DEG C of polymerization reaction 3h, system in whole process
Viscosity does not occur without significant change, polymerization reaction, and the catalyst is without catalytic effect.
Comparative example 2
1) prepare catalyst: equipped with mechanical stirring, nitrogen, thermometer, water segregator four-hole boiling flask in, be added hydroxide
Sodium water solution (60wt%) 11.88g, trifluoro propyl methyl cyclotrisiloxane 84g, dimethylbenzene 60ml are warming up to reflux under stirring,
Solid, which gradually dissolves, forms uniform solution, and the water of generation is azeotroped off using water segregator, after collecting 4.00g water, then constant temperature
1h is reacted, then remaining toluene is evaporated off in normal pressure, and decompression abstraction is low under 60 DEG C, 20mbar waves object, obtains colorless and transparent
Grease.
2) cyclosiloxane polymerize: by 2L planetary mixer after nitrogen is sufficiently displaced from, four silicon of prestox ring being added into kettle
Oxygen alkane 1000g, is dehydrated 1h under 50 DEG C, 10mbar, and then using the broken sky of nitrogen, it is poly- that the end-vinyl that molecular weight is 500 is added
Dimethylsiloxane oligomer 67.57g, above-mentioned catalyst 0.13g, are warming up to 165 DEG C of polymerization reaction 3h, system in whole process
Viscosity does not occur without significant change, polymerization reaction, and the catalyst is without catalytic effect.
The characterization of 1 catalyst of table
Claims (10)
1. a kind of organopolysiloxane catalyst is the trifluoro propyl methyl of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali
Silicon alkoxide, structure are shown below:
Wherein n=3-10, M are the cation of potassium, rubidium, caesium, quaternary ammonium base, season phosphine alkali.
2. the preparation method of organopolysiloxane catalyst described in claim 1, comprising the following steps: alkali metal hydroxide
Or quaternary ammonium base or season phosphine alkali and trifluoro propyl methyl cyclotrisiloxane be at 50-160 DEG C, in water and organic molten at preferably 70-140 DEG C
Reacted in the presence of agent, using the water in solvent azeotropic distillation removing system, then again solvent removed by vacuum and it is low wave object, urged
Agent product.
3. the preparation method of organopolysiloxane catalyst described in claim 1, comprising the following steps:
1) trifluoro propyl methyl cyclotrisiloxane and the aqueous solution of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali are blended in
Together, organic solvent is added, is reacted at 50-160 DEG C, the water of raw material and reaction generation is removed using water segregator, until anhydrous
It generates；
2) solvent removed by vacuum is down to room temperature under nitrogen protection, and product is poured into closed preservation in container.
4. preparation method according to claim 2 or 3, wherein alkali metal hydroxide be potassium hydroxide, rubidium hydroxide,
One of cesium hydroxide is a variety of, preferably potassium hydroxide；And/or
Quaternary ammonium base is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 4 penta
One of base ammonium hydroxide, four hexyl ammonium hydroxide are a variety of, preferably tetramethylammonium hydroxide；And/or
Season phosphine alkali is tetrabutylammonium hydroxide phosphine.
5. preparation method according to claim 2 or 3, wherein the use of alkali metal hydroxide or quaternary ammonium base or season phosphine alkali
Amount is the 6-50wt% of trifluoro propyl methyl cyclotrisiloxane quality；When alkali metal hydroxide, preferably 6-25wt%；This season
When ammonium alkali, preferably 11-40wt%；When this season phosphine alkali, preferably 34-50wt%.
6. preparation method according to claim 2 or 3, wherein organic solvent is benzene,toluene,xylene, n-hexane, ring
One of hexane, chlorobenzene, fluorobenzene, carbon tetrachloride, chloroform, dichloroethanes, ethyl acetate, acetonitrile are a variety of, it is preferable that have
The additive amount of solvent is the 50-200wt%, preferably 80-120wt% of trifluoro propyl methyl cyclotrisiloxane.
7. preparation method according to claim 2 or 3, wherein when using potassium hydroxide, solvent is benzene, toluene, diformazan
One of benzene, n-hexane, hexamethylene are a variety of；
When using tetramethylammonium hydroxide, solvent is toluene；
When using tetrabutylammonium hydroxide phosphine, solvent is dimethylbenzene.
8. the purposes that organopolysiloxane catalyst described in claim 1 is used to be catalyzed the ring-opening polymerization of cyclosiloxane.
9. purposes according to claim 8, wherein cyclosiloxane includes hexamethyl cyclotrisiloxane, four silicon of prestox ring
Oxygen alkane, decamethylcyclopentaandoxane, trimethyl trivinyl cyclotrisiloxane, t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl
One of base tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane are a variety of；
The preferred octamethylcy-clotetrasiloxane of cyclosiloxane, t etram-ethyltetravinylcyclotetrasiloxane, four silicon of tetramethyl tetraphenyl ring
One of oxygen alkane, octamethylcy-clotetrasiloxane are a variety of.
10. purposes according to claim 8, wherein the dosage of catalyst is the 0.01- of monomer cyclosiloxane gross mass
1wt%.
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| WO2021106943A1 (en) * | 2019-11-29 | 2021-06-03 | 日東化成株式会社 | Curing catalyst used for curing of polymer, production method for said curing catalyst, moisture-curable composition, and production method for cured article |
| JPWO2021106942A1 (en) * | 2019-11-29 | 2021-12-02 | 日東化成株式会社 | Moisture-curable composition, manufacturing method of cured product |
| JPWO2021106943A1 (en) * | 2019-11-29 | 2021-12-02 | 日東化成株式会社 | Moisture-curable composition, manufacturing method of cured product |
| JP7048138B2 (en) | 2019-11-29 | 2022-04-05 | 日東化成株式会社 | Moisture-curable composition, manufacturing method of cured product |
| JP7048139B2 (en) | 2019-11-29 | 2022-04-05 | 日東化成株式会社 | Moisture-curable composition, manufacturing method of cured product |
| CN111073303A (en) * | 2019-12-05 | 2020-04-28 | 宁国天运橡塑制品有限公司 | Preparation method of hydrophobic fluorosilicone rubber sealing gasket |
| CN114214027A (en) * | 2021-12-27 | 2022-03-22 | 东莞市正安有机硅科技有限公司 | Non-gel hardening type alkali glue and preparation method thereof |
| CN114214027B (en) * | 2021-12-27 | 2023-05-16 | 东莞市正安有机硅科技有限公司 | Gel-free hardening type alkali gel and preparation method thereof |
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