EP1082327A1 - Perfluorierte organosubstituierte cyclosiloxane und aus diesen cyclosiloxanen hergestellte copolymere - Google Patents

Perfluorierte organosubstituierte cyclosiloxane und aus diesen cyclosiloxanen hergestellte copolymere

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Publication number
EP1082327A1
EP1082327A1 EP99908551A EP99908551A EP1082327A1 EP 1082327 A1 EP1082327 A1 EP 1082327A1 EP 99908551 A EP99908551 A EP 99908551A EP 99908551 A EP99908551 A EP 99908551A EP 1082327 A1 EP1082327 A1 EP 1082327A1
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EP
European Patent Office
Prior art keywords
copolymer
polymerizable
perfluorinated
cyclosiloxanes
cyclosiloxane
Prior art date
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Withdrawn
Application number
EP99908551A
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English (en)
French (fr)
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EP1082327A4 (de
Inventor
Mark A. Buese
John Scott Shaffer
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Clariant LSM Florida Inc
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Archimica Florida Inc
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Publication date
Priority claimed from US09/086,649 external-priority patent/US5914420A/en
Priority claimed from US09/087,185 external-priority patent/US5892086A/en
Application filed by Archimica Florida Inc filed Critical Archimica Florida Inc
Publication of EP1082327A1 publication Critical patent/EP1082327A1/de
Publication of EP1082327A4 publication Critical patent/EP1082327A4/de
Withdrawn legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to the preparation of cyclosiloxanes with one perfluorinated substituent and their ring-opening polymerization into silicone copolymers .
  • silicone polymers and copolymers are via ring-opening polymerization. Most commonly it is carried out by the polymerization of unstrained cyclosiloxanes, generally cyclic tetramers or pentamers, where no heat is generated upon polymerization. Typically the polymer constitutes up to approximately 90 percent of the resulting equilibrium mixture depending upon the substituents on the cyclosiloxane, the degree of polymerization achieved, and the amount of any solvent used in the polymerization. The amount of cyclosiloxanes that have been observed in equilibrium with many silicone polymers is described in Siloxane Polymers, Chapter 3, S.J. Clarson and J.A.
  • Cyclic trimers are strained and the polymerization is exothermic. Cyclic trimers are generally more difficult to prepare than cyclic tetramers and pentamers.
  • the most common fluorinated silicone is prepared by the ring-opening polymerization of 1,3,5-tris- ( 3, 3,3-trifluoro- propyl)-l,3,5-trimethylcyclotrisiloxane.
  • the weight percent of the fluorocarbon portion of the cyclosiloxane and its resulting homo-polymer is 44% by weight.
  • the exothermic polymerization is driven due to the ring strain that is released upon the opening of the cyclic trimer. The polymerization must be stopped immediately after high polymer has formed, otherwise the polymer reverts to a mixture of cyclics, primarily the unstrained tetramer and pentamer which together constitute about 90% by weight of the cyclic mixture.
  • United States Patent No. 5,202,453 describes a strained cyclotrisiloxane with a single fluorinated organic substitutent .
  • This compound was prepared in a two step process from a 1H,1H,2H- vinyl terminated oligomer of hexafluoropropene oxide with a combined yield of approximately 50% based upon the moles of oligomer used.
  • it was suggested to be ring-opening polymerizable in the presence of alkaline or acid catalysts, presumably under conditions similar to those used for the polymerization of l,3,5-tris-( 3,3 , 3- trifluoro-propyl ) -1 , 3 , 5-trimethylcyclotrisiloxane .
  • Unstrained cyclosiloxanes with one or two large substituents on each Si atom typically are difficult to polymerize as the magnitude of a cyclosiloxane ' s equilibrium constant increases relative to that of a cyclosiloxane with smaller substituents, while at the same time the maximum concentration of the Si-0 bond decreases as the size of the substituent increases. These factors result in a very high proportion of cyclosiloxanes at equilibrium as in the case of 1, 3, 5-tris-( 3 , 3, 3-trifluoropropyl) -1,3, 5-trimethylcyclotrisiloxane. Because of this problem, it is common to prepare a silicone polymer with a small reactive group, often a hydrogen substituent, on the backbone.
  • United States Patent No. 5,247,116 describes a method where unstrained cyclosiloxanes with a single functional group can be prepared and subsequently isolated. This functional group may be transformed in a variety of fashions such that a single perfluorinated organic moiety may be introduced to a cyclosiloxane ring.
  • the advantage of such a cyclosiloxane is that the Si-0 bond concentration can be significantly higher than that of cyclo-siloxane with a perfluorinated organic substituent at every Si atom, for an equivalent molecular weight of the cyclosiloxane.
  • One object of the present invention is to provide unstrained polymerizable cyclosiloxanes that have one substituent that contains a perfluorinated organic moiety whose structure is given by the general formula (I):
  • X is a divalent radical which may include 0, NH, N(CH 3 ), 0C(0), NHC(O), N(CH 3 )C(0) and CH 2 ; and
  • R F is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R is a perfluorinated ether radical of the general formula (II):
  • m, n, X, and R F are defined as in formula (I); and q may be 2 to 1,000,000.
  • di-siloxanes and/or their equivalents in polysiloxanes include, but are not exclusive to, hexame thy ldi s i loxane , 1,1,3,3- tetramethyldisiloxane, 1,3-divinyl-l, 1,3,3-tetramethyldisiloxane, 1 , 3-di- ( 3-aminopropyl ) -1 , 1 , 3 , 3-tetramethyldisiloxane , 1 , 3-di ( 3- hydroxypropyl ) -1, 1,3,3-tetramethyldisiloxane, 1,3-di-phenyl- 1,1,3, 3-tetramethyldisiloxane , 1 , 3-di- ( 3-chloropropyl-l , 1,3,3- tetramethyldisiloxane, and 1 , 3-di- ( 3-methacryloxypropyl ) -1
  • the unstrained polymerizable cyclosiloxanes of the present invention are those which have methyl groups at all but one site for substituents. That site contains a perfluorinated organic moiety that may have a variety of molecular weights and functional groups connecting the moiety to the cyclosiloxane ring.
  • the cyclosiloxanes have the general formula (I).
  • the cyclosiloxanes may be produced by a hydrosilation reaction between a mono Si-H containing cyclodimethylsiloxane, such as heptamethyl-cyclotetrasiloxane or nonamethylcyclopentasiloxane, and a IH, 1H,2H-vinyl substituted fluorinated organic molecule.
  • the cyclosiloxane of formula (I) may be produced by reacting an oligomer of hexafluoropropeneoxide of the structure:
  • the mono Si-H containing cyclodimethylsiloxane may undergo hydrosilation with an amine, such as allyl amine or N-methylallyl amine, or an alcohol, such as allyl alcohol, with a terminal vinyl group followed by its reaction with an oligomer of hexafluoropropene ⁇ oxide of formula (IV).
  • an amine such as allyl amine or N-methylallyl amine
  • an alcohol such as allyl alcohol
  • the ester that would result from the reaction between the oligomer of hexafluoropropene oxide of formula (IV) and methanol or ethanol may be used in an amidation or in a trans-esterification reaction to yield the cyclosiloxane of formula (I).
  • the cyclosiloxanes of formula (I) may be polymerized using an acid or alkaline catalyst in a manner typical of unstrained cyclosiloxanes to a mixture of linear copolymer and cyclic oligomers.
  • the choice of catalyst will be dependent upon the nature of the group X in the cyclosiloxane of formula (I) as is known to those skilled in the art.
  • the linear copolymer may be separated from the cyclic oligomers by extraction with a hydrocarbon. The size of the hydrocarbon may vary depending upon the size of the perfluorinated organic moiety.
  • the hydrocarbon will be less than 10 carbons in the chain such that it is sufficiently volatile to be easily removed from the extracted cyclosiloxanes and the copolymer.
  • the resulting copolymer will have the general formula (III).
  • the extracted cyclic oligomers may be repolymerized in like manner to the cyclosiloxanes of formula (I) from whose polymerization mixture it was extracted.
  • the extracted cyclosiloxanes will be of the formula (V) :
  • the degree of polymerization can be controlled by the amount of catalyst used and, to a greater extent, the presence of any chain capping agent which may be included in the polymerization mixture.
  • Capping agents which may be used are typically disiloxanes of the formula (VI):
  • R is H, methyl, ethyl, phenyl, vinyl, hydroxypropy1 , aminopropyl, or any other functional hydrocarbon radical.
  • the cyclosiloxane of formula (I) may be copolymerized with a wide variety of cyclosiloxanes and linear siloxanes.
  • Cyclodimethyl-siloxanes such as octamethylcyclotetrasiloxane or decamethylcyclo-pentasiloxane may be used to produce a copolymer where the ratio of dimethylsiloxy groups to methylperfluoroorganosiloxy group is a value greater than three.
  • Cyclosiloxanes with functional groups can be incorporated to permit specific processing or impart specific properties to the copolymer depending upon the final application of the copolymer as is known to those skilled in the art.
  • Cyclosilox-anes which may be copolymerized with the cyclosiloxane of formula (I) include, but are not exclusive to, those which contain hydrogenmethylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl)methylsiloxy, ( aminopropyl)methylsiloxy, (hydroxy- propyl )methylsiloxy, ( acryloxypropyl ) methylsiloxy , and (methacryl-oxypropyl)methylsiloxy repeating units.
  • EXAMPLE 5 A 3-necked 250 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, and an addition funnel was charged with 34.6 g of 99% (3- h ⁇ droxypropyl)heptamethylcyclotetra-siloxane (101 mmoles) and 17.0 g of K 2 HPO. (97.6 mequivalents ) . The mixture was stirred and 87.6 g of hexafluoropropeneoxide oligomer acid fluoride with an average degree of polymerization of 4.4 (119 mmoles) was added dropwise at a rate such that the temperature did not exceed 40°C.
  • EXAMPLE 6 A 25 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 4.0 g of (3-hydroxy- propyl) heptamethylcyclotetrasiloxane (12 mmoles) and 1.0 g of pyridine (13 mmoles). The mixture was stirred and 5.0 g of per- fluorooctanoyl chloride (12 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid chloride and most of the cyclosiloxane were consumed with one product as 96.5% of the mixture.
  • the contents of the flask were filtered using a 0.45 micron syringe filter into a 50 mL 1-necked round bottom flask.
  • the solids in the flask were washed with 2.5 mL of pentane and this suspension added to the syringe and filtered into the 50 mL flask.
  • the solids in the syringe were washed with an additional 2.5 mL of pentane and filtered into the 50 mL flask.
  • F m is 1, n is 3, X is OC(O), and R is a perfluorinated straight chain monovalent alkyl radical of 7 carbons atoms, or more specifically as shown in formula (VIII) below.
  • the bottom ester layer was removed and the top layer discarded.
  • the bottom ester layer was again placed in the separatory funnel and washed with a 20 mL portion of dilute hydrochloric acid.
  • the ester was removed and subsequently washed with another 20 mL portion of dilute hydrochloric acid and then twice with 20 mL portions of water.
  • the ester was transferred into a round bottom flask and distilled at 62-64 °C and 3 mmHg to yield a fraction of 29.0 g (69% yield) of >99% [3-perfluoro- 2 , 5 , 8-trimethyl-3 , 6 , 9-trioxadodecan-oyl ) oxy] -1-propene ( 41 mmoles) .
  • a 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe.
  • the flask was charged with 10.0 g of >99% [ 3- (perfluoro-2 , 5 , 8-tri- methyl-3,6,9-trioxadecan-oyl)oxy]-l-propene and 4.0 g of heptamethylcyclotetrasiloxane (14 mmoles).
  • the mixture was heated to 80°C and 10 ⁇ L of a Pt 1, 3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via a syringe. The temperature was increased.
  • a 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 9.0 g of allyl amine (160 mmoles).
  • the liquid was stirred and 40 g of 97% perfluoro-2, 5, 8-trimethyl-3, 6, 9-trioxadodecanoyl fluoride (60 mmoles) was added dropwise.
  • Dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the amide layer. The amide layer was washed again with dilute hydrochloric acid and twice with water.
  • the amide layer was transferred into a round bottom flask and distilled at 101°C and 3 mmHg to yield a fraction of 21.6 (52% yield) of >99% N-allylper luoro-2 ,5 , 8- trimethyl-3,6 , 9-trioxado-decanamide (31 mmoles).
  • a 3-necked 25 mL flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe.
  • the flask was charged with 10.0 g of >99% N-allyl-perfluoro-2 ,5,8-trimeth ⁇ l-3, 6 , 9-tri- oxadodecanamide (14 mmoles) and 4.0 g of heptamethylcyclotetrasiloxane (14 mmoles).
  • the mixture was heated to 100°C and 10 ⁇ L of a Pt 1, 3-divinyltetrameth ⁇ ldisiloxane complex in xylene (3% Pt) was added via a syringe.
  • a 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 5.0 g of N- methylallyl amine (70 mmoles).
  • the liquid was stirred and 17.5 g of 97% per-fluoro-2 , 5 , 8-trimethyl-3 , 6 , 9-trioxadodecanoyl fluoride (26 mmoles) was added dropwise.
  • the reaction mixture was transferred into a separatory funnel and the amide layer was washed twice with dilute hydrochloric acid and once with water.
  • the amide layer was trans-ferred into a round bottom flask and distilled at 98°C and 2.4 mmHg to yield a fraction of 14.3 g (77% yield) of >99% N-allyl-N-methyl-perfluoro-2 ,5,8-trimethyl-3, 6 ,9- trioxadodecanamide (20 mmoles).
  • a 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe.
  • the flask was charged with 7.0 g of >99% N-allyl-N-methylperfluoro- 2,5,8-trimethyl-3,6 ,9-trioxadodecanamide (10 mmoles) and 2.8 g of heptamethylcyclotetrasiloxane (10 mmoles).
  • the mixture was heated to 106°C and 10 ⁇ L of a Pt 1 , 3-divinyltetramethyl- disiloxane complex in xylene (3% Pt) was added via a syringe.
  • a 500 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, a condenser, and an addition funnel was charged with 11.0 g of allyl amine (193 mmoles) and 15 g of pyridine (190 mmoles).
  • the liquid was stirred and 150 g of hexa-fluoropropeneoxide oligomer acid fluoride, with a degree of polymerization of 4.4 (205 mmoles) was added dropwise.
  • the contents of the flask were transferred to a separatory funnel and washed twice with dilute hydrochloric acid and subsequently washed twice with water.
  • the amide layer was transferred into a round bottom flask.
  • the product was distilled at 95-190°C and 5.1 mmHg to yield a fraction of 125 g (84% yield) of N-allyl- oligohexafluoropropene-oxide-oyl amide .
  • a 3-necked 250 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe.
  • the flask was charged with 5.0 g of N-allyl-oligohexafluoropropene- oxide-oyl amide (6.5 mmoles) and 30 g of heptamethylcyclotetrasiloxane (106 mmoles).
  • the mixture was heated to 100°C and 30 ⁇ L of a Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) was added via a syringe.
  • the 1.5 dram vial and syringe were rinsed with pentane and the liquid injected through the filter into the 3 dram vial such that an approximately 20% by volume perfluoroethersiloxane mixture in pentane resulted.
  • the two phases were dispersed by shaking and immediately a 3 ⁇ L sample was drawn into a syringe and injected into a gas chromatograph. Signals were observed in the chromatographic trace which had a pattern of four groups of signals. The two groups with the shorter retention time each displayed four narrow well resolved signals which decreased in intensity with increasing retention time. The latter two groups displayed many poorly resolved signals.
  • the retention times of the first group were identical to that of octamethylcyclotetrasiloxane, decamethyl- cyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetra- decamethylcycloheptasiloxane.
  • the largest peak of the second group had the retention time of [ 3-(per-fluoro-2, 5,8, 11- tetramethyl-3 ,6,9, 12-tetraoxapentadecan-oyl ) oxypropyl ]hepta- methylcyclotetrasiloxane.
  • the molar ratio of octamethylcyclotetrasiloxane :decamethylcyclopenta- siloxane should equal K 4 K 4 :K 5 ( 0.75) /K 4 :K 6 (0.75) 2 /K 4 for random placement of siloxane units where the dimethylsiloxane units constitute 75% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
  • the second group consisted of [ 3- (perfluoro-2 ,5,8 , ll-tetramethyl-3 , 6,9, 12-tetraoxapentadecan-oyl ) oxypropyl ]heptamethylcyclotetrasiloxane, [ 3- (perfluoro- 2,5,8, 1l-tetramethyl-3 , 6,9, 12-tetraoxapentadecan-oyl ) oxypropyl ] - nonamethylcyclopentasiloxane , [3-(per-fluoro-2, 5, 8, ll- tetramethyl-3 ,6,9, 12-tetraoxapentadecan-oyl) oxypropyl ]undeca- methylcyclohexasiloxane, and [ 3- (perfluoro-2, 5, 8, ll-tetramethyl- 3,6 , 9 , 12-tetraoxapentadecan-oyl ) oxypropy
  • the upper layer was drawn from the lower layer using a syringe and placed in a scintillation vial.
  • An additional 3 mL of pentane was added to the 3 dram vial containing the lower layer and the vial shaken.
  • the top layer was again removed via a syringe and placed in the scintillation vial.
  • a gas chromatographic trace of the lower layer in the 3 dram vial displayed almost no signals from the equilibrium cyclo ⁇ siloxanes.
  • the pentane swelling the copolymer was removed by heating the vial on a hot plate while passing a stream of nitrogen over the surface. This resulted in 0.6 g of a gum which displayed no flow upon cooling when the vial was placed on its side for a period of 2 hours, indicating that the molecular weight of the copolymer was high.
  • the resulting viscous linear-cyclic mixture was similar in nature to that which resulted from the polymerization of 99% [ 3- ( perfluoro-2 ,5,8, ll-tetramethyl-3 ,6,9, 12-tetraoxapentadecan- oyl) -oxypropyl ] -heptamethylcyclotetrasiloxane in Example 11.
  • EXAMPLE 16 Into a 1.5 dram vial containing 2.0 g of N-( 3-heptamethyl- cyclotetrasiloxan-yl)propyloligohexafluoropropeneoxide-oyl amide (1.7 mmoles) from Example 10 was injected 19.0 ⁇ L of tetrabutyl- ammonium fluoride in tetrahydrofuran (0.019 mmoles) and the mixture was shaken. The vial was warmed gently with a heating gun over a period of 10 minutes. After cooling to room temperature, a viscous mixture was noted.
  • the heating of the vial was repeated 6 times until a heavy oil, that displayed very slow flow when the vial was inverted at room temperature, resulted and no apparent increase in viscosity was observed upon subsequent heating.
  • the oil was warmed again and let stand for 24 hours. The mixture remained clear in appearance at room temperature.
  • the vial was then heated strongly with the formation of bubbles, presumably from the decomposition of the tetrabutylammonium salt with the liberation of tributylamine and butene.
  • a linear-cyclic mixture, similar, in nature to that which resulted in Example 15 was observed by gas chromatographic analysis.
  • EXAMPLE 17 A 3-necked 50 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of IH, lH,2H-perfluoro-1-octene (28.9 mmoles) and 10.0 g of heptamethylcyclotetrasiloxane (35.4 mmoles). The mixture was heated to 90°C and 5 ⁇ L of a Pt 1,3- divinyltetra-methyldisiloxane complex in xylene (3% Pt) was added via a syringe. An exothermic reaction occurred with a rapid increase in temperature to 130°C which cooled after 3 minutes.
  • the product was analyzed by spectroscopy with the following results: H NMR 400 MHz, CDC1 3 : d 0.1 (m 21 H), 0.8 (m 2 H), 2.1 (m 2 H); IR (neat liquid on NaCl): cm “1 : 2970 (m) , 2870 (w) , 1445 (w) , 1405 (w) , 1370 (w) , 1265 (s), 1240 (s), 1205 (m) , 1175 (w) , 1150 (m) , 990 (vs), 810
  • EXAMPLE 18 Into a 1.5 dram vial containing 2.0 g of 99% IH, 1H,2H,2H, 1- (heptamet ylcyclotetrasiloxan-yl)perfluorooctane (3.2 mmoles) from Example 17 was injected 3.0 ⁇ L of trifluoromethanesulfonic acid (0.035 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which displayed almost no flow when the vial was inverted at room temperature, resulted. The gum was warmed again and let stand for 24 hours.
  • the vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which dis-played almost no flow when the vial was inverted at room temp-erature, resulted.
  • the gum was warmed again and let stand for 24 hours.
  • To the vial was added 0.1 g of MgO (2.5 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was observed by gas chromatographic analysis.
  • the molar ratio of octamethylcyclotetrasiloxane : decamethylcyclopentasiloxane : dodecamethylcyclohexa- siloxane should equal K 4 K 4 :K 5 ( 0.997 ) K 4 : -K g ( 0.997 ) 2 /K 4 for random placement of siloxane units where the dimethylsiloxane units constitute 99.7% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
  • the mole ratio of octamethylcyclotetrasiloxane [3- (perfluoro-2, 6, 8, ll-tetramethyl-3, 6 ,9 , 12-tetraoxapenta ⁇ decan-oyl ) oxypropyl ] heptamethylcyclotetrasiloxane was determined to be 100:2 which agreed well with the theoretical ratio of 100:1.2 from the relationship K 4 (0.997) 4 :4K 4 ( 0.997) 3 ( 0.003) for a random polymerization to high molecular weight.
  • the vial was warmed gently with a heating gun and the viscosity increased over a period of 30 minutes. The mixture was warmed again and let stand for 24 hours. To the vial was added 0.02 g of MgO (0.4 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was dissolved in 6 mL of cyclohexane and analyzed by gas chromatography.
  • the molar ratio of octamethylcyclotetrasiloxane : decamethylcyclopentasiloxane :dodecamethylcyclohexasiloxane should equal K 4 /K 4 :K 5 (0.993)/K 4 :K 6 (0.993) 2 /-K 4 for random placement of siloxane units where the dimethyl-siloxane units constitute 99.3% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
  • the vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes.
  • To the vial was added 0.05 g of MgO (1 mmole) .
  • a copolymer-cyclic mixture was dissolved in 3 mL of cyclohexane and analyzed by gas chromatography.
  • the molar ratio of octamethylcyclotetrasiloxane decamethylcyclopentasiloxane : dodecamethylcyclohexasiloxane should equal K 4 K 4 :K 5 ( 0.994) /K 4 :K 5 ( 0.994 ) 2 /K 4 for random placement of siloxane units where the dimethylsiloxane units constitute 99.4% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer as a macromolecule with a degree of polymerization of approximately 200 was targeted by the proportions of cyclosiloxanes to disiloxanes used.

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EP99908551A 1998-05-29 1999-02-26 Perfluorierte organosubstituierte cyclosiloxane und aus diesen cyclosiloxanen hergestellte copolymere Withdrawn EP1082327A4 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US09/086,649 US5914420A (en) 1998-05-29 1998-05-29 Perfluorinated organo substituted cyylosiloxanes and copolymers prepared from these cyclosiloxahes
US09/087,185 US5892086A (en) 1998-05-29 1998-05-29 Perfluorinated ether organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes
US87185 1998-05-29
PCT/US1999/004341 WO1999062916A1 (en) 1998-05-29 1999-02-26 Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes
US86649 2002-03-01

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See also references of WO9962916A1 *

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CA2342153A1 (en) 1999-12-09
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AU2795599A (en) 1999-12-20
EP1082327A4 (de) 2003-04-16

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