Patent GB-1333455-A (GB)
Title: Fluorohexahalogenoisopropoxyalkanoyloxyalkyl silicon derivatives and their polymers and copolymers
Inventor: MEILLER F
IPC: C07F7/18
Filed: 1971-07-05
Abstract: 1333455 Fluorinated silanes and siloxanes PRODUITS CHIMIQUES PECHINEYSAINT-GOBAIN 5 July 1971 [6 July 1970] 31336/71 Headings C3S and C3T [Also in Divisions C2 and C5] Novel organosilicon compounds of the formula wherein each of X 1 , X 2 , X 3 , X<SP>1</SP> 1 , X<SP>1</SP> 2  and X<SP>1</SP> 3  denote halogen, with the proviso that not more than two such symbols denote chlorine atoms, n denotes an integer of from 1 to 18, m denotes an integer of from 2 to 7, and A denotes wherein R 1 , R 2  and R 3  independently denote a saturated or aromatic hydrocarbon group, a hydrolysable group or atom, a hydrogen atom or a fluorohexahalogenoisopropoxyalkanoyloxyalkyl group of the formula  with the proviso that not more than one of these symbols denotes a hydrogen atom and with the further proviso that not more than one of the said symbols denotes a fluorohexahalogenoisopropoxyalkanoyloxyalkyl group as defined above, R 4  denotes hydrogen, alkyl or phenyl, R 5  denotes alkyl, phenyl or a fluorohexahalogenoisopropoxyalkanoyloxyalkyl group of the above formula, and q denotes an integer, are prepared by reacting a silane of the formula or a cyclic siloxane of the formula wherein R<SP>1</SP> 1 , R<SP>1</SP> 2  and R<SP>1</SP> 3  independently denote a saturated or aromatic hydrocarbon group, or a hydrolysable group or atom, or one or two of such symbols may also denote a hydrogen atom, and R<SP>1</SP> 5  denotes a hydrogen atom or an alkyl or phenyl group, with an alkenyl fluoro. hexahalogenoisopropoxyalkylcarboxylate of the formula wherein n<SP>1</SP> denotes zero or an integer of from 1 to 5, in the presence of a chloroplatinic or peroxidic catalyst at a temperature of from 30 to 120 C. for from 4 to 8 hours. Alternatively the above novel compounds may be prepared by reacting the reaction product of an alkali metal fluoride and a hexahalogenoacetone with a halogenoalkanoyloxyalkylsilane of the formula or a cyclic halogenoalkanoyloxyalkylsiloxane of the formula wherein Z denotes Cl, I or Br, each of R<SP>11</SP> 1  R<SP>11</SP> 2  and R<SP>11</SP> 3  independently denote a saturated or aromatic hydrocarbon group, a hydrolysable group or atom, a hydrogen atom or a halogenoalkanoyloxyalkyl group of the formula with the proviso that not more than one of R<SP>11</SP> 1 , R<SP>11</SP> 2  and R<SP>11</SP> 3  may denote a hydrogen atom and with the further proviso that not more than one of R<SP>11</SP> 1 , R<SP>11</SP> 2  and R<SP>11</SP> 3  may denote a halogenoalkanoyloxyalkyl group as defined above, and R<SP>11</SP> 5  denotes an alkyl, phenyl or halogenoalkanoyloxyalkyl group as defined above using temperatures of ambient to 40 C. for from 10 to 150 hours. The invention further comprises polymers and copolymers of the above novel organosilicon compounds. These include (1) dimers of the formula  obtained by hydrolysis of monomers having a single hydrolysable substituent, viz,. R 3 ; (2) mixed dimers of the formula obtained by cohydrolysis of monomers having a single hydrolysable substituent (viz. R 3 ) with conventional silanes of the formula wherein R 6  is a hydrolysable substituent and R 7 , R 8  and R 9  denote hydrogen, alkyl or phenyl; (3) copolymers having a chain composed of monomeric units of the formula and terminal monomeric units of the formula obtained by cohydrolysis of monomers having a single hydrolysable substituent (viz. R 3 ) with a conventional silane having two hydrolysable groups and the formula wherein R 6  and R 10  denote hydrolysable groups; (4) linear polymers and copolymers having a chain of monomeric units of the formula and optional monomeric units of the formula -Si(R 7 R 8 )-O-, obtained by hydrolysis of monomers having two hydrolysable substituents (viz. R 2  and R 3 ) optionally in the presence of conventional silanes having two hydrolysable groups; (5) crosslinked polymers and copolymers comprising monomeric units of the formula and optional monomeric units of the formula obtained by hydrolysis of monomers having three hydrolysable substituents (viz. R 1 , R 2  and R 3 ) optionally in the presence of conventional silanes having three hydrolysable groups and the formula wherein R 6 , R 11  and R 12  denote hydroysable groups; and (6) linear copolymers and copolymers comprising chains of monomeric units of the formula  and optional monomeric units of the formula -O-Si(R 13 R 14 )-, obtained by ring opening cyclic siloxanes optionally in conjunction with conventional cyclic siloxanes of the formula wherein R 13  and R 14  denote hydrogen, alkyl or phenyl and r is zero or an integer of from 1 to 6. Acid catalysts are used to obtain viscous oily polymers according to (6), while basic catalysts produce translucent gums of very high molecular weight. Uses.-Chain limiting agents, polymers and copolymers, lubricants, water and oil-repellent agents for textiles, paper and leather, solventresistant elastomeric gums.