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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silicon Polymers (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=21785660

Family Applications (1)

Country Status (8)

Cited By (3)

Families Citing this family (13)

Citations (1)

Family Cites Families (8)

• 1998
  • 1998-02-03 US US09/017,990 patent/US5892084A/en not_active Expired - Lifetime
• 1999
  • 1999-01-29 WO PCT/US1999/001978 patent/WO1999038872A1/en not_active Ceased
  • 1999-01-29 EP EP99903494A patent/EP1068213B1/en not_active Expired - Lifetime
  • 1999-01-29 DE DE69906716T patent/DE69906716T2/de not_active Expired - Lifetime
  • 1999-01-29 AU AU23501/99A patent/AU2350199A/en not_active Abandoned
  • 1999-01-29 JP JP2000529339A patent/JP2002501925A/ja not_active Withdrawn
  • 1999-01-29 ES ES99903494T patent/ES2194439T3/es not_active Expired - Lifetime
  • 1999-01-29 CA CA002319185A patent/CA2319185A1/en not_active Abandoned

Patent Citations (1)

Also Published As

Similar Documents

Legal Events