CN107936052A - A kind of preparation method of different alkane alkenyloxy group silane - Google Patents
A kind of preparation method of different alkane alkenyloxy group silane Download PDFInfo
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- CN107936052A CN107936052A CN201711157214.XA CN201711157214A CN107936052A CN 107936052 A CN107936052 A CN 107936052A CN 201711157214 A CN201711157214 A CN 201711157214A CN 107936052 A CN107936052 A CN 107936052A
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- Prior art keywords
- alkenyloxy group
- temperature
- group silane
- filtrate
- kettle
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 56
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 54
- 125000003302 alkenyloxy group Chemical group 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000000706 filtrate Substances 0.000 claims abstract description 67
- -1 Alkyl ketone Chemical class 0.000 claims abstract description 50
- 239000012452 mother liquor Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 20
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012188 paraffin wax Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 241000370738 Chlorion Species 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 52
- 230000035484 reaction time Effects 0.000 claims description 23
- 235000011150 stannous chloride Nutrition 0.000 claims description 18
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 10
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229940114926 stearate Drugs 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 4
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 3
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 3
- 229940114930 potassium stearate Drugs 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- WWCOVQNIXCSASL-UHFFFAOYSA-N ethenyl(dimethyl)-lambda3-chlorane Chemical compound C(=C)Cl(C)C WWCOVQNIXCSASL-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000010992 reflux Methods 0.000 abstract description 14
- GBFVZTUQONJGSL-UHFFFAOYSA-N ethenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C=C GBFVZTUQONJGSL-UHFFFAOYSA-N 0.000 description 15
- IVHXEBVFCNBWED-UHFFFAOYSA-N prop-1-en-2-yloxysilane Chemical compound CC(=C)O[SiH3] IVHXEBVFCNBWED-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 8
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical group C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 208000036142 Viral infection Diseases 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical class CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- LWWFOCUDNWWRTJ-UHFFFAOYSA-N CC=C[SiH](Cl)Cl Chemical class CC=C[SiH](Cl)Cl LWWFOCUDNWWRTJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MKDHTPTXOKJEFU-UHFFFAOYSA-N [N].Cl Chemical compound [N].Cl MKDHTPTXOKJEFU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical group OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
- C07F7/20—Purification, separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a kind of preparation method of different alkane alkenyloxy group silane, reactions steps are as follows：Alkyl ketone, acid binding agent and catalyst are put into reaction kettle, the mass ratio of alkyl ketone, acid binding agent and catalyst is 1000:1090:1~5, kettle temperature is heated to while stirring as 40 DEG C；It is 20 DEG C~60 DEG C to keep kettle temperature, and chlorosilane is added dropwise into reaction kettle, and 20min~40min is dripped off, and chlorosilane keeps the temperature reflux after dripping, until different alkane alkenyloxy group silane contents are more than 30% in reaction kettle, closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；The first filtrate is distilled under normal pressure, obtains the first mother liquor；Solid paraffin and chlorion neutralizer are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, reacts 1h~3h, is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；The second filtrate of rectification under vacuum obtains different alkane alkenyloxy group silane, and rectification temperature is 124 DEG C~126 DEG C, and pressure is 0.0130MPa~0.0140MPa.For different alkane alkenyloxy group silane purity prepared by the present invention up to more than 94%, yield is higher than 63%.
Description
Technical field
The present invention relates to a kind of preparation method of different alkane alkenyloxy group silane, particularly different alkane is prepared with alkyl ketone isomerization process
The method of alkenyloxy group silane.
Background technology
Different alkane alkenyloxy group silane is the more special silane crosslinker of a kind of purposes, because containing different alkane alkenyloxy group in molecular structure
And the functional group of alkyl, alkenyl or phenyl, it is widely used in and the polymer such as polyethylene, polypropylene, unsaturated polyester (UP) is changed
Property, and assign its excellent resistance to compression cracking performance, Memorability, wearability and impact；Improve glass fibre, inorganic filler and right
Affinity between the resin of vinyl reaction, is usually used in organosilane cross-linked poly-ethylene cable and tubing ageing resistance；Can be with propylene
Extraordinary exterior coating is made in the coating copolymerization of acid system, has good weatherability, resistant to dust etc.；For the crosslinking curing of silicon rubber,
Itself and metal, fabric interface adhesion properties can be lifted.Especially, in room temperature vulcanized silicone rubber system, dealcoholized type room temperature vulcanized silicon
The heat resistance of rubber is poor；And the heat resistance ratio dealcoholized type of de- ketone type and depickling type room temperature vulcanized silicone rubber is excellent, but depickling
Acid is discharged in type cross-linking process and there is corrosivity and sharp aroma, this makes its application gradually be restricted.Therefore, different alkane alkene
The cross-linking system of epoxide type room temperature vulcanized silicone rubber because its hydrolysing activity highest, cross-linking reaction easily carry out it is thorough, heat-resist,
Curingprocess rate is fast, storage stability, avoid it is premature gelling, extensive without using poisonous organic catalyst, neutral cure
Using, therefore market is increasingly being its demand.
Since aliphatic ketone forms the alcohol of formula structure of isomerization under catalyst action, the K values such as acetone are smaller, because
This, relative amount existing for alcohol of formula structure is very low, it is necessary to which the forward direction movement for accelerating to react using means of catalysis, improves enol form
Concentration.At present, the report in relation to the synthesis of different alkane alkenyloxy group silane is less, and usually using stannous chloride as catalyst, triethylamine is to tie up
Sour agent, makees solvent, the reaction time is up to 20~50h, alkyltrichlorosilanes and alkyl ketone using virose arene compounds
The yield that the different alkane alkenyloxy group silane silane of alkyl is made in reaction is less than 50%.Wherein, there is three isopropyl alkene oxygen of document report vinyl
The yield of base silane is 45.7%, and the yield for also having pertinent literature report three iso-propenyloxysilane of phenyl is 43%, above-mentioned side
Different alkane alkenyloxy group silane prepared by method also has the following disadvantages in addition to yield is low：Made using virose benzene-like compounds molten
Agent, processing safety is low, reaction time length, of high cost, and also needs to high temperature and pressure, is unfavorable for industrialized production and application.
The content of the invention
For defect existing in the prior art, it is an object of the invention to provide a kind of preparation of different alkane alkenyloxy group silane
Method, the different alkane alkenyloxy group silane stay in grade of this method preparation, high income, relative inexpensiveness, and technique is simple, is conducive to
Industrialized production.
To achieve the above objectives, the present invention adopts the technical scheme that：A kind of preparation method of different alkane alkenyloxy group silane, its
Include the following steps：
S1：Alkyl ketone, acid binding agent and catalyst, the mass ratio of alkyl ketone, acid binding agent and catalyst are put into reaction kettle
For 1000:1090:1~5, kettle temperature is heated to while stirring as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, chlorosilane is added dropwise into reaction kettle, 20min~40min is dripped off, chlorosilane
Back flow reaction is kept the temperature after dripping, until different alkane alkenyloxy group silane contents are more than 30% in reaction kettle, closed filtering tertiary amine hydrochloric acid
Salt solid, obtains the first filtrate；The first filtrate is distilled under normal pressure, recycles unreacted alkyl ketone and acid binding agent, it is female to obtain first
Liquid；
S3：Solid paraffin and chlorion neutralizer are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, during reaction
Between be 1h~3h, and then kettle temperature be 35 DEG C~40 DEG C under the conditions of filter, obtain the second filtrate；
S4：The second filtrate of rectification under vacuum obtains different alkane alkenyloxy group silane, and rectification temperature is 124 DEG C~126 DEG C, and pressure is
0.0130MPa~0.0140MPa.
Further, chlorosilane is methyl trichlorosilane, propyltrichlorosilan, vinyl trichlorosilane, phenyl trichlorine silicon
One kind in alkane, methylvinyldichlorosilane, dimethyl vinyl chlorosilane and tetrachloro silicane.
Further, alkyl ketone is one kind in acetone, butanone and pentanone.
Further, catalyst is one kind or more in zinc chloride, nickel chloride, copper chloride, stannous chloride and stannous chloride
Kind.
Further, acid binding agent is triethylamine, tripropyl amine (TPA), tri-n-butylamine, dodecyl-dimethyl amine and etradecyldimethylamine
One or more in amine.
Further, solid paraffin is the one or more in scale wax, semi-refined paraffin wax and fully refined paraffin wax.
Further, chlorion neutralizer be zinc stearate, potassium stearate, calcium stearate and odium stearate in one kind or
It is a variety of.
Further, the mass ratio of the gross mass of acetone, acid binding agent and chlorosilane and solid paraffin is 1：0.05~0.1,
The gross mass of acetone, acid binding agent and chlorosilane is 1 with the mass ratio of chlorion neutralizer：0.01~0.1.
Further, the mass ratio of chlorosilane and catalyst is 1：0.001~0.005.
Further, back flow reaction temperature is 50 DEG C~70 DEG C in S2.
Compared with prior art, the advantage of the invention is that：
(1) present invention uses chlorosilane, for raw material, to pass through the isomerization alcoholysis ester-interchange method of alkyl ketone with alkyl ketone
High different alkane alkenyloxy group silane, its process route is easy, and raw material is cheap and easy to get, and single step reaction can obtain target product, safety
Property it is high, be conducive to industrialized production, while tertiary ammonium salt recoverable, environment had no effect, different alkane alkenyloxy group silicon
For alkane purity up to more than 94%, yield is higher than 63%.
(2) it is both the solvent that substrate also serves as reaction that the present invention, which uses alkyl ketone, avoids using toxic solvent, meanwhile, instead
The alkyl ketone and acid binding agent that Ying Zhongwei has reacted can reuse, and reduce manufacturing cost.
(3) preparation method provided by the invention, the high-temperature high-voltage reaction condition to discard tradition, the different alkane alkenyloxy group silicon of preparation
Alkane product is not stable, easy to change, and without peculiar smell, the simultaneous reactions time is short.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
The embodiment of the present invention provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：Alkyl ketone, acid binding agent and catalyst, the mass ratio of alkyl ketone, acid binding agent and catalyst are put into reaction kettle
For 1000:1090:1~5, kettle temperature is heated to while stirring as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, chlorosilane is added dropwise into reaction kettle, 20min~40min is dripped off, chlorosilane
Back flow reaction is kept the temperature after dripping, until different alkane alkenyloxy group silane contents are more than 30% in reaction kettle, closed filtering tertiary amine hydrochloric acid
Salt solid, obtains the first filtrate；The first filtrate is distilled under normal pressure, recycles unreacted alkyl ketone and acid binding agent, it is female to obtain first
Liquid；
S3：Solid paraffin and chlorion neutralizer are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, during reaction
Between be 1h~3h, and then kettle temperature be 35 DEG C~40 DEG C under the conditions of filter, obtain the second filtrate；
S4：The second filtrate of rectification under vacuum obtains different alkane alkenyloxy group silane, and rectification temperature is 124 DEG C~126 DEG C, and pressure is
0.0130MPa~0.0140MPa.
Preferably whether it is more than 30% by different alkane alkenyloxy group silane contents in gas chromatography analysis reaction kettle in S2, certainly
, other common analysis can also.The alkyl ketone and acid binding agent obtained in S3 can recycle, as next time
Raw material.
Chlorosilane is methyl trichlorosilane, propyltrichlorosilan, vinyl trichlorosilane, phenyl trichlorosilane, methyl second
One kind in alkenyl dichlorosilane, dimethyl vinyl chlorosilane and tetrachloro silicane.
Alkyl ketone is one kind in acetone, butanone and pentanone.
Catalyst is metal chloride, is specially in zinc chloride, nickel chloride, copper chloride, stannous chloride and stannous chloride
It is one or more.It is preferred that use zinc chloride and stannous chloride.
Acid binding agent is tertiary amine, is specifically triethylamine, tripropyl amine (TPA), tri-n-butylamine, dodecyl-dimethyl amine and cetyl
One or more in dimethylamine.It is preferred that use tripropyl amine (TPA).
Solid paraffin is the one or more in scale wax, semi-refined paraffin wax and fully refined paraffin wax.Its mechanism of action is
Tertiary ammonium salt during load adsorption reaction, can significantly reduce viscosity, be conducive to reaction mass transfer.
Chlorion neutralizer is stearate, specifically, chlorion neutralizer is zinc stearate, potassium stearate, stearic acid
One or more in calcium and odium stearate.It is preferred that zinc stearate is used, it is highly preferred that selection potassium phthalimide,
The tertiary amine that can be dissolved in efficient process product, avoids different alkane alkenyloxy group silane from occurring unstable, easy to change and have peculiar smell defect.
The mass ratio of acetone, the gross mass of acid binding agent and chlorosilane and solid paraffin is 1：0.05~0.1, acetone, tie up acid
The mass ratio of the gross mass of agent and chlorosilane and chlorion neutralizer is 1：0.01~0.1.
The mass ratio of chlorosilane and catalyst is 1：0.001~0.005.
Back flow reaction temperature is 50 DEG C~70 DEG C in S2.
The present invention is described in further detail below in conjunction with 13 embodiments and 1 comparative example, comparative example is using existing
It is prepared by preparation scheme.
Embodiment 1
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 224g triethylamines and 0.224g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 20min~25min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 50 DEG C, reaction time 48h, until reaction
Vinyltriisopropenyloxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted acetone and triethylamine, obtains the first mother liquor；
S3：28.4g scale waxs and 5.68g zinc stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, instead
It is 2h between seasonable, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains vinyltriisopropenyloxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0130MPa.
In the present embodiment, the vinyltriisopropenyloxysilane content in step S4 cuts is 97.5%, total chloridion
Less than 50ppm, yield 71.9%.
Embodiment 2
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g tripropyl amine (TPA)s and 0.45g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 150g vinyl trichlorosilanes, 30min~40min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 70 DEG C, reaction time 48h, until reaction
Vinyltriisopropenyloxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted acetone and tripropyl amine (TPA), obtains the first mother liquor；
S3：30.9g semi-refined paraffin waxs and 61.8g zinc stearates are added into the first mother liquor, it is 40 DEG C~60 to keep kettle temperature
DEG C, reaction time 1h, and then filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtain the second filtrate；
S4：The second filtrate of rectification under vacuum obtains vinyltriisopropenyloxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0138MPa.
In the present embodiment, the vinyltriisopropenyloxysilane content in step S4 cuts is 97.2%, total chloridion
Less than 50ppm, yield 66.6%.
Embodiment 3
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g tri-n-butylamines and 2.34g nickel chlorides are disposably put into reaction kettle, is heated while stirring
It it is 40 DEG C to kettle temperature；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 30min~40min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 58 DEG C, reaction time 48h, until reaction
Vinyltriisopropenyloxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted acetone and tri-n-butylamine, obtains the first mother liquor；
S3：57g fully refined paraffin wax and 5.7g potassium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature,
Reaction time is 3h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains vinyltriisopropenyloxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0138MPa.
In the present embodiment, the vinyltriisopropenyloxysilane content in step S4 cuts is 97.2%, total chloridion
Less than 50ppm, yield 69.5%.
Embodiment 4
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 1.87g copper chlorides are disposably put into reaction kettle, is heated while stirring
It it is 40 DEG C to kettle temperature；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 25min~30min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 50 DEG C, reaction time 48h, until reaction
Vinyltriisopropenyloxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted acetone and triethylamine, obtains the first mother liquor；
S3：45.6g scale waxs and 57g potassium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, reaction
Time is 1h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, then heats up and distillation obtains the second filtrate under normal pressure；
S4：The second filtrate of rectification under vacuum obtains vinyltriisopropenyloxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0140MPa.
In the present embodiment, the vinyltriisopropenyloxysilane content in step S4 cuts is 97.7%, total chloridion
Less than 50ppm, yield 66.5%.
Embodiment 5
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g dodecyl-dimethyl amines and 0.47g stannous chlorides are disposably put into reaction kettle,
Kettle temperature is heated to while stirring as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g phenyl trichlorosilanes, 25min~30min drops are added dropwise into reaction kettle
Complete, phenyl trichlorosilane keeps the temperature back flow reaction after dripping, and reflux temperature is 50 DEG C, reaction time 48h, until in reaction kettle
Three iso-propenyloxysilane content of phenyl is more than 30%, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Steamed under normal pressure
The first filtrate is evaporated, unreacted acetone and dodecyl-dimethyl amine is recycled, obtains the first mother liquor；
S3：28.5g scale waxs and 17.1g zinc stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, instead
It is 2h between seasonable, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains three iso-propenyloxysilane of phenyl, and rectification temperature is 124 DEG C~126 DEG C, pressure
Strong is 0.0138MPa.
In the present embodiment, the three iso-propenyloxysilane content of phenyl in step S4 cuts is 95.5%, and total chloridion is small
In 50ppm, yield 68.0%.
Embodiment 6
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g hexadecyidimethylamines and 2.34g copper chlorides are disposably put into reaction kettle, while stirring
Mix side and be heated to kettle temperature as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 25min~30min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 58 DEG C, reaction time 48h, until reaction
Vinyltriisopropenyloxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted acetone and hexadecyidimethylamine, obtains the first mother liquor；
S3：28.5g scale waxs and semi-refined paraffin wax mixture and 28.5g potassium stearates are added into the first mother liquor, is protected
Kettle temperature is held as 40 DEG C~60 DEG C, reaction time 3h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filter
Liquid；
S4：The second filtrate of rectification under vacuum obtains vinyltriisopropenyloxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0140MPa.
In the present embodiment, the vinyltriisopropenyloxysilane content in step S4 cuts is 97.2%, total chloridion
Less than 50ppm, yield 63.0%.
Embodiment 7
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 2.34g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g methyl trichlorosilanes, 25min~30min drops are added dropwise into reaction kettle
Complete, methyl trichlorosilane keeps the temperature back flow reaction after dripping, and reflux temperature is 55 DEG C, reaction time 48h, until in reaction kettle
Three iso-propenyloxysilane content of methyl is more than 30%, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Steamed under normal pressure
The first filtrate is evaporated, unreacted acetone and triethylamine is recycled, obtains the first mother liquor；
S3：57g scale waxs and 40g calcium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, during reaction
Between be 2h, and then kettle temperature be 35 DEG C~40 DEG C under the conditions of filter, obtain the second filtrate；
S4：The second filtrate of rectification under vacuum obtains three iso-propenyloxysilane of methyl, and rectification temperature is 124 DEG C~126 DEG C, pressure
Strong is 0.0138MPa.
In the present embodiment, the three iso-propenyloxysilane content of methyl in step S4 cuts is 98.1%, and total chloridion is small
In 50ppm, yield 71.3%.
Embodiment 8
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 0.57g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g propyltrichlorosilans, 25min~30min drops are added dropwise into reaction kettle
Complete, propyltrichlorosilan keeps the temperature back flow reaction after dripping, and reflux temperature is 65 DEG C, reaction time 48h, until in reaction kettle
Three iso-propenyloxysilane content of propyl group is more than 30%, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Steamed under normal pressure
The first filtrate is evaporated, unreacted acetone and triethylamine is recycled, obtains the first mother liquor；
S3：45.6g scale waxs and 51.3g odium stearate are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, instead
It is 2h between seasonable, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains three iso-propenyloxysilane of propyl group, and rectification temperature is 124 DEG C~126 DEG C, pressure
Strong is 0.0138MPa.
In the present embodiment, the three iso-propenyloxysilane content of propyl group in step S4 cuts is 98.2%, and total chloridion is small
In 50ppm, yield 71.7%.
Embodiment 9
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 1.71g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, the dropwise addition 100g methylvinyldichlorosilanes into reaction kettle, 25min~
30min is dripped off, and methylvinyldichlorosilane keeps the temperature back flow reaction after dripping, and reflux temperature is 58 DEG C, and the reaction time is
48h, until methyl ethylene diisopropyl alkenyloxy group silane contents are more than 30% in reaction kettle, closed filtering Amine from Tertiary Amine Hydrochloride is consolidated
Body, obtains the first filtrate；The first filtrate is distilled under normal pressure, unreacted acetone and triethylamine is recycled, obtains the first mother liquor；
S3：28.5g scale waxs and 57g calcium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, reaction
Time is 2h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains methyl ethylene diisopropyl alkenyloxy group silane, rectification temperature for 124 DEG C~
126 DEG C, pressure 0.0138MPa.
In the present embodiment, the methyl ethylene diisopropyl alkenyloxy group silane contents in step S4 cuts are 96.6%, total chlorine
Ion is less than 50ppm, yield 66.4%.
Embodiment 10
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 0.57g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, the dropwise addition 100g dimethyl vinyl chlorosilanes into reaction kettle, 25min~
30min is dripped off, and dimethyl vinyl chlorosilane keeps the temperature back flow reaction after dripping, and reflux temperature is 58 DEG C, and the reaction time is
48h, until dimethyl ethenyl iso-propenyloxysilane content is more than 30% in reaction kettle, closed filtering Amine from Tertiary Amine Hydrochloride is consolidated
Body, obtains the first filtrate；The first filtrate is distilled under normal pressure, unreacted acetone and triethylamine is recycled, obtains the first mother liquor；
S3：40g scale waxs and 5.7g calcium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, reaction
Time is 2h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains dimethyl ethenyl iso-propenyloxysilane, rectification temperature for 124 DEG C~
126 DEG C, pressure 0.0138MPa.
In the present embodiment, the dimethyl ethenyl iso-propenyloxysilane content in step S4 cuts is 99.1%, total chlorine
Ion is less than 50ppm, yield 83.7%.
Embodiment 11
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g acetone, 244g triethylamines and 0.57g stannous chlorides are disposably put into reaction kettle, is added while stirring
Heat to kettle temperature is 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g tetrachloro silicanes are added dropwise into reaction kettle, and 25min~30min is dripped off,
Tetrachloro silicane keeps the temperature back flow reaction after dripping, reflux temperature is 58 DEG C, reaction time 48h, until four isopropyls in reaction kettle
Alkenyloxy group silane contents are more than 30%, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；The filter of distillation first under normal pressure
Liquid, recycles unreacted acetone and triethylamine, obtains the first mother liquor；
S3：51.3g scale waxs and 57.9g potassium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, instead
It is 2h between seasonable, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains four iso-propenyloxysilanes, and rectification temperature is 124 DEG C~126 DEG C, and pressure is
0.0138MPa。
In the present embodiment, four iso-propenyloxysilane contents in step S4 cuts are 94.45%, and total chloridion is less than
50ppm, yield 69.8%.
Embodiment 12
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g butanone, 244g triethylamines and 2.3g stannous chlorides are disposably put into reaction kettle, is heated while stirring
It it is 40 DEG C to kettle temperature；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 25min~30min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 58 DEG C, reaction time 48h, until reaction
Vinyl triisobutylene oxysilane content is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted butanone and triethylamine, obtains the first mother liquor；
S3：28.5g scale waxs and 5.7g potassium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, instead
It is 2h between seasonable, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains vinyl triisobutylene oxysilane, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0138MPa.
In the present embodiment, the vinyl triisobutylene oxysilane content in step S4 cuts is 96.8%, total chloridion
Less than 50ppm, yield 67.5%.
Embodiment 13
The present embodiment provides a kind of preparation method of different alkane alkenyloxy group silane, it includes the following steps：
S1：224g propiones, 244g triethylamines and 0.46g stannous chlorides are disposably put into reaction kettle, while stirring
Kettle temperature is heated to as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and 100g vinyl trichlorosilanes, 25min~30min are added dropwise into reaction kettle
Drip off, vinyl trichlorosilane keeps the temperature back flow reaction after dripping, reflux temperature is 58 DEG C, reaction time 48h, until reaction
Three iso-amylene oxysilane content of vinyl is more than 30% in kettle, and closed filtering Amine from Tertiary Amine Hydrochloride solid, obtains the first filtrate；Often
Pressure the first filtrate of distillation, recycles unreacted propione and triethylamine, obtains the first mother liquor；
S3：57g scale waxs and 5.7g potassium stearates are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, reaction
Time is 2h, and then is filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtains the second filtrate；
S4：The second filtrate of rectification under vacuum obtains three iso-amylene oxysilane of vinyl, and rectification temperature is 124 DEG C~126 DEG C,
Pressure is 0.0138MPa.
In the present embodiment, the three iso-amylene oxysilane content of vinyl in step S4 cuts is 99.0%, total chloridion
Less than 50ppm, yield 85.2%.
Comparative example 1
In the glass lined high-pressure reaction vessels of 2L, 100g benzene, 250g triethylamines, 232g acetone, the anhydrous chlorinations of 1g are added
Zinc and 120g methyl trichlorosilanes, are warming up to 110 DEG C under stirring, react 16h, then filter off triethylamine under the protection of dry nitrogen
Hydrochloride (320g), filtrate are fractionated through depressurizing (under 2.67kPa) again, collect the 83g crude products of 73 DEG C of cuts.Add 8g activity
Keep 4h to remove remaining HCl at charcoal, with 50 DEG C~60 DEG C, obtain refractive index as 1.4246 purpose product, content 97%,
Yield 47.6%.
The present invention is not limited to the above-described embodiments, for those skilled in the art, is not departing from
On the premise of the principle of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as the protection of the present invention
Within the scope of.The content not being described in detail in this specification belongs to the prior art known to professional and technical personnel in the field.
Claims (10)
1. a kind of preparation method of different alkane alkenyloxy group silane, it is characterised in that it includes the following steps：
S1：Alkyl ketone, acid binding agent and catalyst, the mass ratio of alkyl ketone, acid binding agent and catalyst are put into reaction kettle is
1000:1090:1~5, kettle temperature is heated to while stirring as 40 DEG C；
S2：It is 20 DEG C~60 DEG C to keep kettle temperature, and chlorosilane is added dropwise into reaction kettle, and 20min~40min is dripped off, and chlorosilane is added dropwise
Insulation back flow reaction after complete, until different alkane alkenyloxy group silane contents are more than 30% in reaction kettle, closed filtering Amine from Tertiary Amine Hydrochloride is consolidated
Body, obtains the first filtrate；The first filtrate is distilled under normal pressure, recycles unreacted alkyl ketone and acid binding agent, obtains the first mother liquor；
S3：Solid paraffin and chlorion neutralizer are added into the first mother liquor, it is 40 DEG C~60 DEG C to keep kettle temperature, and the reaction time is
1h~3h, and then filtered under the conditions of being 35 DEG C~40 DEG C in kettle temperature, obtain the second filtrate；
S4：The second filtrate of rectification under vacuum obtains different alkane alkenyloxy group silane, and rectification temperature is 124 DEG C~126 DEG C, and pressure is
0.0130MPa~0.0140MPa.
2. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Chlorosilane is methyl trichlorine silicon
Alkane, propyltrichlorosilan, vinyl trichlorosilane, phenyl trichlorosilane, methylvinyldichlorosilane, dimethyl ethenyl chlorine
One kind in silane and tetrachloro silicane.
3. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Alkyl ketone is acetone, butanone
With one kind in pentanone.
4. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Catalyst is zinc chloride, chlorine
Change the one or more in nickel, copper chloride, stannous chloride and stannous chloride.
5. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Acid binding agent is triethylamine, three
One or more in propylamine, tri-n-butylamine, dodecyl-dimethyl amine and hexadecyidimethylamine.
6. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Solid paraffin for scale wax,
One or more in semi-refined paraffin wax and fully refined paraffin wax.
7. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Chlorion neutralizer is tristearin
One or more in sour zinc, potassium stearate, calcium stearate and odium stearate.
8. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Acetone, acid binding agent and chlorine silicon
The gross mass of alkane and the mass ratio of solid paraffin are 1：0.05~0.1, the gross mass and chlorion of acetone, acid binding agent and chlorosilane
The mass ratio of neutralizer is 1：0.01~0.1.
9. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：The matter of chlorosilane and catalyst
Amount is than being 1：0.001~0.005.
10. the preparation method of different alkane alkenyloxy group silane as claimed in claim 1, it is characterised in that：Back flow reaction temperature in S2
For 50 DEG C~70 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
| CN109796487A (en) * | 2018-12-14 | 2019-05-24 | 浙江开化合成材料有限公司 | A kind of synthetic method of vinyltriisopropenyloxysilane |
| CN112375097A (en) * | 2020-11-24 | 2021-02-19 | 江西晨光新材料股份有限公司 | Synthetic method of isopropenyl oxotrimethylsilane |
Citations (1)
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| US20050059835A1 (en) * | 2003-09-12 | 2005-03-17 | Honeywell International Inc. | Methods of refining silane compounds |
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2017
- 2017-11-20 CN CN201711157214.XA patent/CN107936052A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050059835A1 (en) * | 2003-09-12 | 2005-03-17 | Honeywell International Inc. | Methods of refining silane compounds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
| CN109796487A (en) * | 2018-12-14 | 2019-05-24 | 浙江开化合成材料有限公司 | A kind of synthetic method of vinyltriisopropenyloxysilane |
| CN112375097A (en) * | 2020-11-24 | 2021-02-19 | 江西晨光新材料股份有限公司 | Synthetic method of isopropenyl oxotrimethylsilane |
| CN112375097B (en) * | 2020-11-24 | 2023-05-05 | 江西晨光新材料股份有限公司 | Synthetic method of isopropenyl oxo-trimethylsilane |
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