WO1999038872A1 - Novel aminoorganofunctionalsiloxanes - Google Patents
Novel aminoorganofunctionalsiloxanes Download PDFInfo
- Publication number
- WO1999038872A1 WO1999038872A1 PCT/US1999/001978 US9901978W WO9938872A1 WO 1999038872 A1 WO1999038872 A1 WO 1999038872A1 US 9901978 W US9901978 W US 9901978W WO 9938872 A1 WO9938872 A1 WO 9938872A1
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- WO
- WIPO (PCT)
- Prior art keywords
- methyl
- process according
- monohydridomethylsiloxane
- isomeric purity
- allylamine
- Prior art date
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- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 3-aminopropylmethylsiloxanes Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 14
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 9
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- SNYNNFDVNITLRQ-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-1,3,5,7,2,4,6,8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 SNYNNFDVNITLRQ-UHFFFAOYSA-N 0.000 claims description 2
- XYHVIYLMNRLZTB-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propan-1-amine Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCN)O[Si](C)(C)O1 XYHVIYLMNRLZTB-UHFFFAOYSA-N 0.000 claims description 2
- KWQQHTNSJIJFBO-UHFFFAOYSA-N 3-[methyl-bis(trimethylsilyloxy)silyl]propan-1-amine Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)CCCN KWQQHTNSJIJFBO-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims 2
- GVTBSSCBPFKFMQ-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8,10,10-nonamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecan-2-yl)propan-1-amine Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(CCCN)O[Si](C)(C)O1 GVTBSSCBPFKFMQ-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- 239000000047 product Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 2
- UCJHMXXKIKBHQP-UHFFFAOYSA-N dichloro-(3-chloropropyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCCCl UCJHMXXKIKBHQP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000005048 methyldichlorosilane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MVDKZIOZIWKNCP-UHFFFAOYSA-N trimethyl-[phenyl(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[SiH](O[Si](C)(C)C)C1=CC=CC=C1 MVDKZIOZIWKNCP-UHFFFAOYSA-N 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- BGPBZMJYENZIMI-UHFFFAOYSA-N 1-[phenyl-bis(trimethylsilyloxy)silyl]propan-2-amine Chemical compound CC(N)C[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 BGPBZMJYENZIMI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- WFUFROXTHMRQMB-UHFFFAOYSA-N 2-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propan-1-amine Chemical compound NCC(C)[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 WFUFROXTHMRQMB-UHFFFAOYSA-N 0.000 description 1
- VFYAYGBOSWNMGA-UHFFFAOYSA-N 3-[bis(trimethylsilyloxy)methylsilyl]propan-1-amine Chemical compound C[Si](C)(C)OC(O[Si](C)(C)C)[SiH2]CCCN VFYAYGBOSWNMGA-UHFFFAOYSA-N 0.000 description 1
- FNVCMFDUMKLCTC-UHFFFAOYSA-N 3-methylsilylpropan-1-amine Chemical class C[SiH2]CCCN FNVCMFDUMKLCTC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GNVPGBIHGALKRR-UHFFFAOYSA-N dichloro-methyl-propylsilane Chemical compound CCC[Si](C)(Cl)Cl GNVPGBIHGALKRR-UHFFFAOYSA-N 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C07F7/0834—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
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
-
- 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
-
- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Definitions
- the present invention relates to high purity 3- aminopropylmethylsiloxanes and a method for their preparation. More specifically, the present invention relates to more than 85% pure 3-aminopropylmethylsiloxane fluids, both linear and cyclic, prepared by hydrosilylation of allylamine by the corresponding hydridomethylsiloxane fluids. These 3-aminopropylmethylsiloxane fluids have utility as intermediates for other derivative organofunctionalsiloxanes , and in cosmetics, textiles, coatings and adhesives.
- 3- Chloropropylmethyl-dichlorosilane may then be alkoxylated, typically with methanol or ethanol, to form the corresponding 3- chloropropylmethyldialkoxy-silanes, in high yield, with formation of hydrochloric acid as the by-product.
- the 3- chloropropylmethyldialkoxysilane may then be converted to the corresponding 3-aminopropylmethyldialkoxysilane by ammonolysis, with requires high pressure equipment since ammonia is used both as a reactant and a solvent. Even with a large excess of
- British Patent No. 2,185,984 describes a synthesis of aminopropylsiloxanes , in approximately a 75% yield, by hydrosilylation of various ketimines, such as N- 2 (butylidene) allyl-amine, with bis ( trimethylsiloxy)methylsilane, followed by hydrolysis.
- the resultant product is a mixture of 71-63% 3-aminopropyl- and 29-37% 2-aminopropyl- substituted siloxanes, indicating that this hydrosilylation process does not produce a single isomeric product. Separation of these isomers, by distillation, is difficult and the overall yield of the 3-(3- aminopropyl ) heptamethyltrisiloxane is only slightly better than 50%.
- each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5.
- the yield of 3-aminopropylmethylsiloxanes from the present invention is greater than about 85%.
- the present invention also provides a simple method for rapidly producing 3-aminopropylmethylsiloxanes of the general formulae
- each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl and x may range from about 3 to about 5, the method comprising hydrosilylating allylamine with the corresponding hydridomethylsiloxanes of the general formulae, HRSi(OSiMe 2 R) 2
- each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and x may range from about 3 to about 5, using a neutral platinum catalyst.
- the present invention provides greater than 85% purity 3-aminopropylmethylsiloxanes of the general formulae: H 2 NCH 2 CH 2 CH 2 RSi(OSiMe 2 R) 2
- each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl and x may range from about 3 to about 5.
- the 3-aminoorganofunctionalsiloxanes of the present invention are prepared by hydrosilylating an allylamine with the corresponding monohydridomethylsiloxane of the general formulae
- Monohydridomethylsiloxanes suitable for use in the process of the present invention, and methods for their preparation are well known to those skilled in the art. Specific examples include, but are not limited to, b i s ( t r i m e t h y l s i l o x y ) m e t h y l s i l a n e , bis ( trimethylsiloxy ) phenylsilane , pentamethyldisiloxane , eptamethylcyclotetrasiloxane and nonamethylcyclopentasiloxane.
- the preferred unsaturated amine is allylamine.
- the hydrosilylation reaction may be carried out at temperatures ranging from about 40°C to about 150°, preferably between about 65°C and about 95°C, in the presence of a catalyst.
- the catalysts that are known in the art are preferably comprised of platinum or complexes of platinum. They include, but are not limited to, c loroplatinic acid, platinum acetylacetonate, complexes of platinous halides with unsaturated compounds such as ethylene, propylene, organovinylsiloxanes and styrene, hexamethyldiplatinum, PtCl 2 , PtCl 3 , Pt(CN) 3 , and mixtures of any of the foregoing.
- the preferred catalyst is platinum complexed with tetravinyltetramethylcyclotetrasiloxane as disclosed in United States Patent Nos . 3,775,452 and 3,814,730.
- platinum catalyst should be used to provide an effective hydrosilylation reaction.
- the preferred amount of platinum catalyst used in the process of the present invention ranges from about 5 to about 150 parts by weight of platinum per million parts of combined weights of siloxane and unsaturated amine .
- Variations of the present invention will suggest themselves to those skilled in the art in light of the above- detailed description.
- a mixture of monohydridomethylsiloxanes, of the above-described types could be used to hydrosilylate allylamine to produce a mixture of 3- aminopropylmethylsiloxanes . All such modifications are within the full intended scope of the appended claims.
- a 100 ml flask was equipped with a magnetic stirrer, reflux condenser, pot thermometer, addition funnel and a sampling port.
- the flask was loaded with 31 g (0.51 mole) of polymethylhydrosiloxane and 36 g (0.63 mole) of allylamine and heated to reflux (62°C). Once at reflux, 330 ⁇ L of 3 % Pt complexed with tetravinlytetramethylcyclotetrasiloxane was added.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Polymers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides high purity 3-aminopropylmethylsiloxanes of general formulae (I) and (II), wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5, the process comprising hydrosilylating allylamine with a monohydridomethylsiloxane of general formulae (III) and (IV), wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group with 1 to about 18 carbon atoms, and x may range from about 3 to about 5, in the presence of a neutral platinum catalyst.
Description
NOVEL AMINOORGANOFUNCTIONALSILOXANES
FIELD OF THE INVENTION
The present invention relates to high purity 3- aminopropylmethylsiloxanes and a method for their preparation. More specifically, the present invention relates to more than 85% pure 3-aminopropylmethylsiloxane fluids, both linear and cyclic, prepared by hydrosilylation of allylamine by the corresponding hydridomethylsiloxane fluids. These 3-aminopropylmethylsiloxane fluids have utility as intermediates for other derivative organofunctionalsiloxanes , and in cosmetics, textiles, coatings and adhesives.
BACKGROUND OF THE PRESENT INVENTION
There is considerable prior art relating to the synthesis of 3-aminopropylmethylsilanes and siloxanes. United States Patent No. 4,736,049 describes the hydrosilylation of allyl chloride by methyldichlorosilane to produce 3- chloropropylmethyldichlorosilane in 79% yield. In the prior art of producing aminoorganofunctional-silanes as intermediates for silicones, allyl chloride is hydro-silylated with methyldichlorosilane. Significant amounts of by-products are formed in this reaction, including methyltrichloro-silane, propylmethyldichlorosilane and propene, necessitating distillation to purify the desired product. 3- Chloropropylmethyl-dichlorosilane may then be alkoxylated, typically with methanol or ethanol, to form the corresponding 3- chloropropylmethyldialkoxy-silanes, in high yield, with formation of hydrochloric acid as the by-product. The 3- chloropropylmethyldialkoxysilane may then be converted to the corresponding 3-aminopropylmethyldialkoxysilane by ammonolysis, with requires high pressure equipment since ammonia is used both as a reactant and a solvent. Even with a large excess of
1
ammonia, formation of the secondary amine, bis (dialkoxymethylsilyl-propyl ) amine occurs to a significant degree, diminishing the yield of the desired primary amine. Filtration of the by-product ammonium chloride is also required in this process .
British Patent No. 2,185,984 describes a synthesis of aminopropylsiloxanes , in approximately a 75% yield, by hydrosilylation of various ketimines, such as N- 2 (butylidene) allyl-amine, with bis ( trimethylsiloxy)methylsilane, followed by hydrolysis. The resultant product is a mixture of 71-63% 3-aminopropyl- and 29-37% 2-aminopropyl- substituted siloxanes, indicating that this hydrosilylation process does not produce a single isomeric product. Separation of these isomers, by distillation, is difficult and the overall yield of the 3-(3- aminopropyl ) heptamethyltrisiloxane is only slightly better than 50%.
European Patent No. 0 321 174 states that aminopropylsiloxanes can be prepared by hydrosilylation of allylamine with an organohydrogensiloxane in the presence of a base and a rhodium catalyst. Our attempts to duplicate this process failed.
A simple high yielding process for producing 3-amino- propylsiloxanes , substantially free of isomeric 2-aminopropyl- siloxanes, has clearly been sought for years to no avail.
SUMMARY OF THE INVENTION
The present invention provides greater than about 85% purity, preferably greater than about 95% purity, of 3- aminopropylmethylsiloxanes of the general formulae:
H2NCH2CH2CH2RSi ( 0SiMe2R) 2
H2NCH2CH2CH2RSiO- ( RMeSiO)- -|
L wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1
to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5. The yield of 3-aminopropylmethylsiloxanes from the present invention is greater than about 85%.
The present invention also provides a simple method for rapidly producing 3-aminopropylmethylsiloxanes of the general formulae
H2NCH2CH2CH2RSi(OSiMe2R)2
H2NCH2CH2CH2RSiO- ( RMeSiO-r.
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl and x may range from about 3 to about 5, the method comprising hydrosilylating allylamine with the corresponding hydridomethylsiloxanes of the general formulae, HRSi(OSiMe2R)2
HRSiO-(RMeSiO)—
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, and x may range from about 3 to about 5, using a neutral platinum catalyst.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides greater than 85% purity 3-aminopropylmethylsiloxanes of the general formulae: H2NCH2CH2CH2RSi(OSiMe2R)2
H2NCH2CH2CH2RSiO- ( RMeSi07
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl and x may range from about
3 to about 5.
The 3-aminoorganofunctionalsiloxanes of the present invention are prepared by hydrosilylating an allylamine with the corresponding monohydridomethylsiloxane of the general formulae
HRSi(OSiMe2R)2
HRSiO-(RMeSiO)—
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5, in the presence of a neutral platinum catalyst, such as Karsted ' s .
Monohydridomethylsiloxanes suitable for use in the process of the present invention, and methods for their preparation are well known to those skilled in the art. Specific examples include, but are not limited to, b i s ( t r i m e t h y l s i l o x y ) m e t h y l s i l a n e , bis ( trimethylsiloxy ) phenylsilane , pentamethyldisiloxane , eptamethylcyclotetrasiloxane and nonamethylcyclopentasiloxane.
The preferred unsaturated amine is allylamine. The hydrosilylation reaction may be carried out at temperatures ranging from about 40°C to about 150°, preferably between about 65°C and about 95°C, in the presence of a catalyst.
The catalysts that are known in the art are preferably comprised of platinum or complexes of platinum. They include, but are not limited to, c loroplatinic acid, platinum acetylacetonate, complexes of platinous halides with unsaturated compounds such as ethylene, propylene, organovinylsiloxanes and styrene, hexamethyldiplatinum, PtCl2, PtCl3, Pt(CN)3, and mixtures of any of the foregoing. The preferred catalyst is platinum complexed with tetravinyltetramethylcyclotetrasiloxane as disclosed in United States Patent Nos . 3,775,452 and 3,814,730.
Sufficient platinum catalyst should be used to provide an effective hydrosilylation reaction. The preferred amount of
platinum catalyst used in the process of the present invention ranges from about 5 to about 150 parts by weight of platinum per million parts of combined weights of siloxane and unsaturated amine . Variations of the present invention will suggest themselves to those skilled in the art in light of the above- detailed description. For example, a mixture of monohydridomethylsiloxanes, of the above-described types, could be used to hydrosilylate allylamine to produce a mixture of 3- aminopropylmethylsiloxanes . All such modifications are within the full intended scope of the appended claims.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples illustrate the present invention. They are not to be construed to limit the scope of the appended claims in any manner whatsoever.
EXAMPLE 1
A 100 ml flask equipped with magnetic stirring, reflux condenser, pot thermometer, and sampling port was charged with 15 g (0.26 mole) of allylamine and 60 g (0.27 mole) of bis ( trimethylsiloxy )methylsilane and was then heated to reflux (69°C). Once at reflux, 225 μl of 3% Pt complexed with tetravinyltetramethylcyclotetrasiloxane was added. The pot temperature exothermed to 95°C, where it was maintained for 3 hr. The reaction was shown by GC analysis to be complete, resulting in 100% reaction of the allylamine. Excess bis ( trimethylsiloxy )methylsilane was distilled off and the product was flash distilled at 80°C at 10 mm Hg pressure. The product, 3-aminopropyl-bis ( trimethylsiloxy)methylsilane, was obtained in a 95% distilled yield based on allylamine. The product's identity was confirmed by GC Mass Spectrometry, H NMR, and FTIR. The 3-aminoproyl- to 2-aminopropyl- isomer ratio of the products was 19/1.
EXAMPLE 2
In a 250 ml 3-neck RB flask equipped with a magnetic stirring bar, a thermometer well and thermometer, a glass stopper and a reflux condenser, was placed 15.5 g (272 mmoles) of allyl amine and 85.6 g (290 mmoles) of 97% heptamethylcyclotetrasiloxane . The mixture was heated to reflux (80°C) and 120 μl of platinum 1 , 3-divinyltetramethyldisiloxane complex (5% Pt) was added. After 70 minutes an exothermic reaction occurred and the temperature increased to 100°C. After 150 minutes a gas chromatographic analysis indicated that all of the allyl amine was consumed and a 7.3:1 ratio of addition products resulted which were assigned after analysis by proton nuclear magnetic resonance as the isomers: 3-amino- propylheptamethylcyclotetras i loxane and 2-amino-l- methylethylheptamethylcyclotetrasiloxane, respectively. A simple distillation at 91-92°C and 3.3 mm Hg yielded 64 g (175 mmoles) of 88% pure 3-aminopropylheptamethylcyclotetrasiloxane. The distillation pot residue was approximately 30% of the product by gas chromatographic analysis. 1H NMR 400 MHz, CDC13: δ : 0.05 (M 21 H), 0.5 (m 2 H) , 0.95* (d 0.1 H), 1.15 (s 2 H) , 1.55 (m 2 H) , 2.65 (m 2 H) where all signals are for the major isomer except
* for a small amount of the minor isomer; IR (neat liquid on NaCl): cm"1: 3420 (vw), 3290 (vw), 2970 (s), 2910 (m) , 2850 (w) , 1615 (vw), 1565 (vw), 1440 (vw), 1405 (w) , 1270 (vs), 1080 (vs), 805 (vs), 750 (vw), 710 (w) .
EXAMPLE 3
A 100 ml flask was equipped with a magnetic stirrer, reflux condenser, pot thermometer, and a sampling port. The flask was loaded with 30 g (0.105 mole) of bis ( trimethylsiloxy)phenylsilane and 6 g (0.105) mole of allylamine and heated to reflux (79°C). 180 μl of 3 % Pt complexed with tetravinyltetramet ylcyclotetrasiloxane were added. The mixture was heated to 125 °C and held for one hour.
Thirty one grams (86%) of 3 - ami opr opy 1 - bis (trimethylsiloxy)phenylsilane were produced. None of the isomeric 2-aminopropyl-bis ( trimethylsiloxy)phenylsilane was formed. COMPARATIVE EXAMPLE A
A 250 ml flask was equipped with a magnetic stirrer, reflux condenser, pot thermometer, addition funnel, and a sampling port. The flask was loaded with 26 g of xylene, 0.0775 g of RhCl3 trihydrate, and 0.0705 g of NaOH powder and heated to 130°C. The addition funnel was loaded with 31 g of a polymethylhydrosiloxane (0.52 mole SiH) and 36 g (0.63 mole) of allylamine. At a pot temperature of 130°C, the mixture was added at a rate to maintain a constant temperature. As soon as the mixture was added, an immediate evolution of hydrogen was observed. The reaction mixture gelled. No product could be isolated from the gel .
COMPARATIVE EXAMPLE B
A 100 ml flask was equipped with a magnetic stirrer, reflux condenser, pot thermometer, addition funnel and a sampling port. The flask was loaded with 31 g (0.51 mole) of polymethylhydrosiloxane and 36 g (0.63 mole) of allylamine and heated to reflux (62°C). Once at reflux, 330 μL of 3 % Pt complexed with tetravinlytetramethylcyclotetrasiloxane was added.
Evolution of hydrogen was observed throughout the reaction. The reaction mixture eventually gelled and no product could be isolated from the gel.
COMPARATIVE EXAMPLE C
A 100 ml flask was equipped with a magnetic stirrer, reflux condenser, pot thermometer, addition funnel, and a sampling port. The flask was loaded with 13 g (0.22 mole) of tetramethylcyclotetrasiloxane and heated to 100°C. 110 μl of 3
% Pt complexed with tetravinyltetramethylcyclotetrasiloxane were added to the pot. The addition funnel was charged with 9.7 g (0.17 mole) of allylamine. The allylamine addition was exothermic and the reaction temperature reached 120°C. The reaction mixture gelled and no product could be isolated from the gel .
All of the above-referenced patents, publications and test methods are hereby incorporated by reference.
Many variations of the present invention will suggest themselves to those skilled in the art in light of the above- detailed description. All such modifications are within the full intended scope of the appended claims.
Claims
1. A process for the preparation of greater than 85% isomeric purity 3-aminoorganopropylmethylsiloxanes , said process comprising hydrosilylating an allylamine with a monohydridomethylsiloxane in the presence of a neutral platinum catalyst .
2. A process as defined in Claim 1 wherein said monohydridomethylsiloxane is selected from those of the general formulae :
HRSi(OSiMe2R)2
HRSiO-(RMeSiO
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group with 1 to about 18 carbon atoms, Me is methyl and x may range from about 3 to about 5.
3. A process for the preparation of greater than 85% isomeric purity 3-aminopropylmethylsiloxanes of the general formula :
H2NCH2CH2CH2RSi(OSiMe2R)2
H2NCH2CH2CH2RSiO- ( RMeSiO
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5, said process comprising hydrosilylating allylamine with a monohydridomethylsiloxane of the general formulae:
HRSi(OSiMe2R)2
HRSiO-(RMeSiO -
wherein R, Me and x are as defined above, in the presence of a neutral platinum catalyst.
4. A process according to Claim 3 wherein the monohydridomethylsiloxane is selected from the group consisting o f b i s ( tr imet hyl s i l oxy ) methyl s i l a ne , heptamethylcyclotetrasiloxane, nonamethylcyclopentasiloxane, and mixtures of any of the foregoing.
5. A process according to Claim 3 wherein said platinum catalyst is a complex of platinous chloride and divinyltetramethyl-disiloxane .
6. A process according to Claim 3 wherein said platinum catalyst is a complex of platinous chloride and 1,3,5,7- tetravinyltetramethylcyclotetrasiloxane .
7. A process according to Claim 3 wherein the platinum catalyst is present in an amount ranging from about 5 to about 150 parts by weight of platinum per million parts of combined weights of monohydridomethylsiloxane and allylamine.
10
8. A process according to Claim 3 wherein said hydrosilylation reaction is carried out at a temperature ranging from about 40┬░C to about 150┬░C.
9. A process according to Claim 8 wherein said hydrosilylation reaction is carried out at a temperature ranging from about 65┬░C to about 95┬░C.
10. A composition comprising greater than 85% isomeric purity 3-aminoorganofunctionalsiloxane produced by the process according to Claim 1.
11. A composition as defined in Claim 10 having greater than 85% isomeric purity 3-aminopropylmethylsiloxane.
12. A composition comprising greater than 85% isomeric purity 3-aminopropylmethylsiloxane of the general formula
H2NCH2CH2CH2RSi ( OSiMe2R) 2
H_NCH_CH CH_RSiO- ( RMeSiO)-
wherein each R may be the same or different aryl group, or monovalent straight or branched chain alkyl group having from 1 to about 18 carbon atoms, Me is methyl, and x may range from about 3 to about 5, and produced by the process according to Claim 3.
13. A composition according to Claim 12 wherein each R is methyl .
14. A high purity 3- ( 3-aminopropyl ) heptamethyltri- siloxane according to Claim 13 having an isomeric purity greater than 95%.
15. A composition according to Claim 12 wherein each R is methyl and x ranges from 3 to 4.
16. A high purity 3-aminopropylheptamethylcyclotetra- siloxane according to Claim 15 wherein x is 3 and having an isomeric purity greater than 85%.
11
17. A high purity 3-aminopropylnonamethylcyclopenta- siloxane according to Claim 15 wherein x is 4 and having an isomeric purity greater than 85%.
12
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69906716T DE69906716T2 (en) | 1998-02-03 | 1999-01-29 | SILOXANES WITH AMINO ORGANIC FUNCTIONAL GROUP |
| AU23501/99A AU2350199A (en) | 1998-02-03 | 1999-01-29 | Novel aminoorganofunctionalsiloxanes |
| CA002319185A CA2319185A1 (en) | 1998-02-03 | 1999-01-29 | Novel aminoorganofunctionalsiloxanes |
| JP2000529339A JP2002501925A (en) | 1998-02-03 | 1999-01-29 | New amino organofunctional siloxanes |
| EP99903494A EP1068213B1 (en) | 1998-02-03 | 1999-01-29 | Novel aminoorganofunctionalsiloxanes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/017,990 US5892084A (en) | 1998-02-03 | 1998-02-03 | Aminoorganofunctionalsiloxanes |
| US09/017,990 | 1998-02-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999038872A1 true WO1999038872A1 (en) | 1999-08-05 |
Family
ID=21785660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/001978 WO1999038872A1 (en) | 1998-02-03 | 1999-01-29 | Novel aminoorganofunctionalsiloxanes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5892084A (en) |
| EP (1) | EP1068213B1 (en) |
| JP (1) | JP2002501925A (en) |
| AU (1) | AU2350199A (en) |
| CA (1) | CA2319185A1 (en) |
| DE (1) | DE69906716T2 (en) |
| ES (1) | ES2194439T3 (en) |
| WO (1) | WO1999038872A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001310940A (en) * | 2000-03-22 | 2001-11-06 | Clariant Life Molecules Florida Inc | Poly disiloxane containing amino group |
| JP2001335585A (en) * | 2000-03-22 | 2001-12-04 | Clariant Life Molecules Florida Inc | Poly (aminoalkylsiloxane) |
| WO2006026245A1 (en) * | 2004-08-25 | 2006-03-09 | Johnson & Johnson Vision Care, Inc. | Process for the production of (trimethylsilyloxy)silylalkylglycerol methacrylates |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0927735A1 (en) * | 1998-01-02 | 1999-07-07 | Hüls Aktiengesellschaft | Process for the production of non-reactive aminosilicone oils |
| JP4509247B2 (en) * | 1999-04-30 | 2010-07-21 | 東レ・ダウコーニング株式会社 | Silicone-containing polyimide resin, silicone-containing polyamic acid and method for producing them |
| US6118014A (en) * | 1999-07-16 | 2000-09-12 | Dow Corning Corporation | Organofunctional cocyclic siloxanes |
| US6207781B1 (en) * | 1999-08-20 | 2001-03-27 | Dow Corning Corporation | Polymerization of an organofunctional cocyclic siloxane |
| US6177583B1 (en) * | 1999-08-30 | 2001-01-23 | United Chemical Technologies, Inc. | Method for the preparation of aminopropyl or aminoalkyl functional polyalkyl or aryl siloxanes |
| CN100351314C (en) * | 2005-04-28 | 2007-11-28 | 陈俊光 | Water-proofing agent of water based type organic silicon resin and preparation process thereof |
| CN101024652B (en) * | 2007-03-23 | 2010-05-19 | 广州天赐有机硅科技有限公司 | Method for preparing amino-hydrocarbyl-trisiloxane |
| JP6236202B2 (en) * | 2009-05-01 | 2017-11-22 | ナノシス・インク． | Matrix with functional groups for dispersion of nanostructures |
| US9139770B2 (en) | 2012-06-22 | 2015-09-22 | Nanosys, Inc. | Silicone ligands for stabilizing quantum dot films |
| TWI596188B (en) | 2012-07-02 | 2017-08-21 | 奈米系統股份有限公司 | Highly luminescent nanostructures and methods of producing same |
| WO2014159927A2 (en) | 2013-03-14 | 2014-10-02 | Nanosys, Inc. | Method for solventless quantum dot exchange |
| WO2016102578A1 (en) | 2014-12-23 | 2016-06-30 | Momentive Performance Materials Gmbh | Aminosiloxanes of high purity |
| EP4065630A1 (en) * | 2019-11-26 | 2022-10-05 | Dow Silicones Corporation | Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes |
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|---|---|---|---|---|
| US5026890A (en) * | 1988-05-20 | 1991-06-25 | General Electric Company | Method and intermediates for preparation of bis(aminoalkyl)polydiorganosiloxanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3814730A (en) * | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
| US3775452A (en) * | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
| US4481364A (en) * | 1983-09-26 | 1984-11-06 | Union Carbide Corporation | Preparation of aminopropyltrialkoxysilanes and/or aminoalkylalkoxysilanes |
| JPS61205287A (en) * | 1985-03-08 | 1986-09-11 | Toshiba Silicone Co Ltd | Proudction of amino group-containing organic silicon compound |
| GB8602226D0 (en) * | 1986-01-30 | 1986-03-05 | Dow Corning Ltd | Preparation of primary aminosiloxanes |
| JPH0633288B2 (en) * | 1986-10-06 | 1994-05-02 | 東レ・ダウコ−ニング・シリコ−ン株式会社 | Addition reaction method |
| JPH0796555B2 (en) * | 1987-12-14 | 1995-10-18 | 東燃株式会社 | Method for producing aminopropylsilyl compound |
| DE4344082C1 (en) * | 1993-12-23 | 1994-12-22 | Goldschmidt Ag Th | Process for the preparation of organopolysiloxanes containing secondary aminoalkyl groups bonded to silicon via carbon |
-
1998
- 1998-02-03 US US09/017,990 patent/US5892084A/en not_active Expired - Lifetime
-
1999
- 1999-01-29 JP JP2000529339A patent/JP2002501925A/en not_active Withdrawn
- 1999-01-29 ES ES99903494T patent/ES2194439T3/en not_active Expired - Lifetime
- 1999-01-29 CA CA002319185A patent/CA2319185A1/en not_active Abandoned
- 1999-01-29 EP EP99903494A patent/EP1068213B1/en not_active Expired - Lifetime
- 1999-01-29 AU AU23501/99A patent/AU2350199A/en not_active Abandoned
- 1999-01-29 DE DE69906716T patent/DE69906716T2/en not_active Expired - Lifetime
- 1999-01-29 WO PCT/US1999/001978 patent/WO1999038872A1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026890A (en) * | 1988-05-20 | 1991-06-25 | General Electric Company | Method and intermediates for preparation of bis(aminoalkyl)polydiorganosiloxanes |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001310940A (en) * | 2000-03-22 | 2001-11-06 | Clariant Life Molecules Florida Inc | Poly disiloxane containing amino group |
| JP2001335585A (en) * | 2000-03-22 | 2001-12-04 | Clariant Life Molecules Florida Inc | Poly (aminoalkylsiloxane) |
| WO2006026245A1 (en) * | 2004-08-25 | 2006-03-09 | Johnson & Johnson Vision Care, Inc. | Process for the production of (trimethylsilyloxy)silylalkylglycerol methacrylates |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002501925A (en) | 2002-01-22 |
| ES2194439T3 (en) | 2003-11-16 |
| EP1068213A4 (en) | 2001-05-02 |
| DE69906716T2 (en) | 2003-10-23 |
| EP1068213A1 (en) | 2001-01-17 |
| AU2350199A (en) | 1999-08-16 |
| DE69906716D1 (en) | 2003-05-15 |
| EP1068213B1 (en) | 2003-04-09 |
| US5892084A (en) | 1999-04-06 |
| CA2319185A1 (en) | 1999-08-05 |
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