JP2002517402A - Perfluorinated organo-substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes - Google Patents

Abstract

(57) [Summary] Formula (I): (Wherein m is an integer from 1 to 12; n is an integer from 1 to 4; X is a divalent group such as O, NH, N (CH ₃ ), OC (O), NHC (O ) is _{N (CH 3) C (O} ) and CH _2, and R ^F is, or is perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F is, General formula (II): Wherein R is a perfluorinated ether group wherein p is an integer from 1 to 10), and a copolymer composition prepared from these cyclopolysiloxanes. And copolymer compositions prepared from these cyclosiloxanes and other siloxanes.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the preparation of cyclosiloxanes having monoperfluorinated substituents and their ring-opening polymerization to silicone copolymers.

BACKGROUND OF THE INVENTION One of the most important methods of preparing silicone polymers and copolymers is by ring opening polymerization. Most commonly, it is carried out by the polymerization of unconstrained cyclosiloxanes, which are generally cyclic tetramers or pentamers, wherein no heat is generated during the polymerization. Typically, the polymer will constitute up to about 90% of the resulting equilibrium mixture, depending on the substituents on the cyclosiloxane, the degree of polymerization achieved and the amount of any solvent used in the polymerization. The amount of cyclosiloxane observed during equilibration with multiple silicone polymers was determined by Siloxane Polymer
s, Chapter 3, SJ Clarson and JA Semlyen, ed., Ellis Horwood- PTR Ren
tis Hall, Englewood Cliffs, NJ, 1993. The polymerization can also be performed on cyclic trimers. The cyclic trimer is constrained and the polymerization is exothermic. Cyclic trimers are generally more difficult to prepare than cyclic tetramers and pentamers.

[0003] The most common fluorinated silicones are 1,3,5, -tris- (3,3,3-
It is prepared by ring-opening polymerization of (trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane. The weight percent of the fluorocarbon portion of the cyclosiloxane and the resulting homopolymer is 44% by weight. Exothermic polymerization
It is driven due to ring strain that is released when the ring is opened. The polymerization must be stopped immediately after the formation of the high polymer, otherwise the polymer will form a cyclic material which is mainly unconstrained tetramers and pentamers which together make up about 90% by weight of the cyclic mixture. Return to the mixture.

[0004] US Pat. No. 5,202,453 discloses constrained cyclotrisiloxanes having a single fluorinated organic substituent. This compound is composed of hexafluoropropene oxide 1H, 1H, with a combined yield of about 50% based on moles of oligomer used.
Prepared from the 2H-vinyl terminated oligomer in a two-step procedure. Although not demonstrated in the patent, but in the presence of an alkaline or acidic catalyst, perhaps 1,3
It is suggested that this is a ring opening polymerization under conditions similar to those used for the polymerization of 5, -tris- (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane. Was.

[0005] Unconstrained cyclosiloxanes having one or two large substituents on each Si atom typically have a magnitude of equilibrium constant of the cyclosiloxane that is lower than that of a cyclosiloxane having a small substituent. However, at the same time, the maximum concentration of Si—O bonds decreases as the size of the substituent increases. These factors, as in the case of 1,3,5, -tris- (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, result in a very high ratio of This produces siloxane. Because of this problem, it is common to prepare silicone polymers with small reactive groups, often hydrogen substituents, on the backbone. Hydrosilation of olefins with Si-H containing compounds is often used to prepare organically substituted siloxanes.

[0006] This hydrosylation is often difficult to perform when the solubility of the substituted groups on the siloxane backbone is low in the Si-H containing silicone polymer. Often S
i-H containing polymers contain sites where Si-H has undergone hydrolysis to Si-OH during its preparation, storage, or during the hydrosilation reaction if water is present. Such units may allow for the formation of a branch or gel during the hydrosylation reaction. Perfluorinated organic molecules often exhibit very low miscibility in silicone polymers. The hydrosilation reaction often does not proceed to complete conversion of the olefin or silane reactant. For these reasons, it is difficult to achieve a perfluorinated organic substituted silicone polymer by modification of a functional silicone polymer without structural loss due to incomplete reaction or from the starting Si-H containing polymer. .

[0007] US Pat. No. 5,247,116 describes a method in which unconstrained cyclosiloxanes having a single functional group are prepared and subsequently isolated. This functionality can be converted in various ways so that a single perfluorinated organic moiety can be introduced into the cyclosiloxane ring.
An advantage of such cyclosiloxanes is that the Si—O bond concentration is significantly higher for cyclosiloxanes of equal molecular weight than for cyclosiloxanes having perfluorinated organic substituents at all Si atoms. Furthermore, the equilibrium cyclization constants for the majority of the resulting cyclosiloxanes are still close to those of cyclodimethylsiloxane. This results in a very large fraction of linear siloxanes at equilibrium during the polymerization of the cyclosiloxanes, even when the starting cyclosiloxanes are unconstrained.

SUMMARY OF THE INVENTION One object of the present invention is to provide a compound of the general formula (I):

[0009]

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Wherein m is an integer from 1 to 12; n is an integer from 1 to 4; X is a divalent group such as O, NH, N (CH ₃ ), OC (O), NHC (O), N (CH ₃ ) C (O)
And CH ₂ , and R ^F is a perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F has the general formula (II):

[0011]

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Wherein p is an integer of 1 to 10 and is a perfluorinated ether group and has a monosubstituted polymerizable cyclosiloxane containing a perfluorinated organic moiety. To provide.

[0013] Copolymers resulting from the ring opening polymerization of the cyclosiloxane of formula (I) are prepared to give a general formula (III):

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[0014] (wherein, m, n, X and R ^F is obtained by the same equation as that (I); and q is 2～1,000,0
It is an object of the present invention to obtain a copolymer (which may be 00).

[0015] Copolymers from cyclosiloxanes of formula (I) and cyclodimethylsiloxanes and / or polydimethylsiloxanes such that the resulting copolymers contain a smaller proportion of fluorinated siloxane groups than cyclosiloxanes of formula (I) Preparation is an object of the present invention.

In addition to the siloxy repeat units present in the cyclosiloxane of the formula (I), other siloxy repeat units, such as hydrogen methylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl) methylsiloxy, (aminopropyl It is an object of the present invention to prepare fluorinated silicones containing (but not limited to) methylsiloxy, (hydroxypropyl) methylsiloxy and (trifluoropropyl) methylsiloxy units. These units can be incorporated by the addition of a suitable cyclosiloxane containing one or more of these groups.

It is an object of the present invention to prepare copolymers from the cyclosiloxanes of formula (I), and optionally other cyclosiloxanes, wherein the degree of polymerization is controlled by end capping. This is achieved by equilibrating the appropriate cyclosiloxane with the disiloxane or disiloxane equivalent incorporated in the small polysiloxane. A wide variety of disiloxanes in polysiloxanes and / or their equivalents are known, examples of which include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3 -Divinyl-1,1
, 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) -1,1,3,3-tetramethyldisiloxane and 1,3-di- (3-methacryloxy Propyl) -1,1,3,3-tetramethyldisiloxane and mixtures of any of the foregoing.

DETAILED DESCRIPTION OF THE INVENTION The unconstrained polymerizable cyclosiloxanes of the present invention have a methyl group at all but one site for a substituent. The moiety has a perfluorinated organic moiety having various molecular weights and a functional group linking the moiety to the cyclosiloxane ring.

[0019] The cyclosiloxane has the general formula (I). Cyclosiloxane is mono-Si
-H containing cyclodimethylsiloxanes, such as heptamethylcyclotetrasiloxane or nonamethylcyclopentasiloxane, can be formed by the hydrosilation reaction between 1H, 1H, 2H-vinyl substituted fluorinated organic molecules.

The cyclosiloxane of formula (I) has the structural formula:

[0021]

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Reacting an oligomer of hexafluoropropene oxide (where p is an integer from 1 to 10) with an amine or alcohol and an organic molecule containing a terminal vinyl group, followed by a mono-Si-H containing cyclodimethyl It can be produced by hydrosilation between the amide or ester with a disiloxane. Alternatively, the mono-Si-H containing cyclodimethylsiloxane can be prepared by hydrosilation using an amine having a terminal vinyl group, such as allylamine or N-methylallylamine, or an alcohol such as allyl alcohol, followed by hexafluoropropene of formula (IV). The oxide may undergo its reaction with an oligomer. In some cases, the ester resulting from the reaction between the oligomer of hexafluoropropene oxide of formula (IV) and methanol or ethanol is used in an amidation or in a trans-esterification reaction to form a compound of formula (IV) The cyclosiloxane of I) is produced.

The cyclosiloxane of formula (I) can be polymerized to a mixture of linear copolymers and cyclic oligomers using an acidic or alkaline catalyst in the typical manner of unconstrained cyclosiloxanes. The choice of catalyst depends on the nature of the X group in the cyclosiloxane of formula (I), as is known to those skilled in the art. The linear copolymer is separated from the cyclic oligomer by extraction with a hydrocarbon. The size of the hydrocarbon may vary depending on the size of the perfluorinated organic moiety. Generally, the hydrocarbons will have less than 10 carbon atoms in the chain so that they are volatile enough to be easily removed from the extracted cyclosiloxanes and copolymers. The resulting copolymer has the general formula (III). The extracted cyclic oligomer can be repolymerized in a similar manner to the cyclosiloxane of formula (I) from which it was extracted from the polymerization mixture. The extracted cyclosiloxane has the formula (
V):

[0024]

Embedded image (Where n, X and ^RF are the same as in formula (I), r + s = t,
And t is 4 to 20 and r is 1 to t).

[0025] The degree of polymerization may be controlled by the amount of catalyst used and, to a greater extent, by the presence of any chain capping agents that may be included in the polymerization mixture. Capping agent that may be used is typically given by the formula (VI): R-Si ( CH 3) 2 OSi (CH 3) in ₂ -R (wherein, R is H, methyl, ethyl, phenyl, vinyl, hydroxy Propyl, aminopropyl or any other functional hydrocarbon group). The choice of disiloxane will depend on the particular formulation of the resulting copolymer selected for the end use of the copolymer, as is known to those skilled in the art.

The cyclosiloxane of formula (I) can be copolymerized with a wide variety of cyclosiloxanes and linear siloxanes. Cyclodimethylsiloxanes, such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane, may be used to form the copolymer, wherein the ratio of dimethylsiloxy groups to methylperfluoroorganosiloxy groups is a value greater than 3. Cyclosiloxanes with functional groups can be incorporated, depending on the end use of the copolymer, to allow for specific processing or to impart specific properties to the copolymer, as is known to those skilled in the art. Examples of the cyclosiloxane copolymerizable with the cyclosiloxane of the formula (I) include hydrogen methylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl) methylsiloxy, (aminopropyl) methylsiloxy, and (hydroxypropyl) methylsiloxy. , (Acryloxypropyl)
Methylsiloxy and those containing (methacryloxypropyl) methylsiloxy repeat units include, but are not limited to.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The practice of the present invention is illustrated by the examples of catabolism, but the invention is not limited thereto. These examples are provided for illustrative purposes only, and are not intended to limit the scope of the claims in any way.

Example 1 A 50 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 7.7 g of 98% (
3-Hydroxypropyl) heptamethylcyclotetrasiloxane (22 mmol) and 2.3 g of triethylamine (23 mmol) were charged. Stir the mixture, 15.0 g
Of 97% perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (21.9 mmol) was added dropwise. After complete addition of the oxyfluoride, gas chromatographic analysis indicated that essentially all the oxyfluoride and most of the cyclosiloxane had been consumed, mainly with the formation of one product. 25 of diluted hydrochloric acid
A mL portion was added to the flask, the biphasic mixture was transferred to a separatory funnel and the aqueous layer was separated from the siloxane layer. Wash the siloxane layer with two 25 mL portions of water, transfer the siloxane layer to a 50 mL round bottom flask, distill at 110 ° C. and 0.3 mm Hg to obtain 14.7 g (
97% of 3- (perfluoro-2,5,8-trimethyl-3,6,9).
-Trioxadodecanoyl) oxypropyl] heptamethylcyclotetrasiloxane (14.3 mmol) was obtained, which was of the formula (I) where m is 1 and n
Is 3, X is OC (O), and R ^F is according to formula (II), wherein p is 3, especially the following formula (VII), wherein p is 3 )).

The product was analyzed by spectroscopy with the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (s 21H), 0.6 (t 2H), 1.8 (p 2H), 4.4 (m 2H); ¹⁹ F NMR 376 MH
z, CDCl ₃ : d -81 (CF ₃ ), -82 (CF ₃ ), -83 (CF ₃ ), -85 (CF ₃ ), -130 (CF ₂ ),
-132 (CF ₂ ), -144 (CF); IR (net liquid in NaCl): cm ^-1 : 2970 (m
), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 9
70 (s), 810 (vs), 750 (m).

[0030]

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Example 2 A 50 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 6.2 g of 98% (
3-Hydroxypropyl) heptamethylcyclotetrasiloxane (18 mmol) and 1.8 g of triethylamine (18 mmol) were charged. Stir the mixture, 15.0 g
95% perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl fluoride (17 mmol) was added dropwise. After complete addition of the oxyfluoride, gas chromatographic analysis indicated that essentially all the oxyfluoride and most of the cyclosiloxane had been consumed, mainly with the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask, the biphasic mixture was transferred to a separatory funnel and the aqueous layer was separated from the siloxane layer. Wash the siloxane layer with two 25 mL portions of water and transfer the siloxane layer to a 50 mL round bottom flask at 118-28 ° C and 0.05 m
Distillation at mHg yielded 14.0 g (71% yield) of 99% [3- (perfluoro-2,5,8
, 11-Tetramethyl-3,6,9,12-tetraoxapentadecanoyl) oxypropyl] heptamethylcyclotetrasiloxane (12.2 mmol), which was obtained according to the formula (I) m is 1, n is 3, X is OC (O), and R ^F is according to formula (II), wherein p is 4, especially formula (VII)
) (Where p is 4).

Analysis of the product by spectroscopy gave the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (s 21H), 0.6 (t 2H), 1.8 (p 2H), 4.4 (m 2H); IR (net liquid in NaCl): cm ⁻¹ : 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 114
5 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).

Example 3 A 50 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 5.1 g of 98% (
3-Hydroxypropyl) heptamethylcyclotetrasiloxane (15 mmol) and 1.5 g of triethylamine (15 mmol) were charged. Stir the mixture, 15.0 g
92% of perfluoro-2,5,8,11,14-pentamethyl-3,6,9,1
2,15-Tetraoxaoctadecanoyl fluoride (14 mmol) was added dropwise.
After complete addition of the oxyfluoride, gas chromatographic analysis indicated that essentially all the oxyfluoride and most of the cyclosiloxane had been consumed, mainly with the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask, the biphasic mixture was transferred to a separatory funnel and the aqueous layer was separated from the siloxane layer. Wash the siloxane layer with two 25 mL portions of water, transfer the siloxane layer to a 50 mL round bottom flask, and store at 128-38 ° C.
And distilled at 0.05 mm Hg to give 13.0 g (71% yield) of> 99% [3- (perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxa [Octadecanoyl) oxypropyl] heptamethylcyclotetrasiloxane (14.1 mmol) was obtained, which was of the formula (I) where m is 1 and n is 3
Wherein X is OC (O) and R ^F is represented by formula (II), wherein p is 5, especially in formula (VII), wherein p is 5 Is like that).

The product was analyzed by spectroscopy with the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (s 21H), 0.6 (t 2H), 1.8 (p 2H), 4.4 (m 2H); IR (net liquid in NaCl): cm ⁻¹ : 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 114
5 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).

Example 4 0.5 g of 98% (3-hydroxypropyl) heptamethylcyclotetrasiloxane (1.5 mmol) was placed in five different 10 mL round bottom flasks equipped with a magnetic stir bar and fitted with a rubber septum. And a part of the inorganic base as shown in Table 1 was added to the four flasks. All bases were used as accepted and were> 98% pure. The mixture was stirred and 1.2 g of 95% perfluoro-2,5,8,11
Tetramethyl-3,6,9,12-tetraoxapentadecanoyl fluoride (1.4 mmol) with an additional 25 G needle placed on the septum to ensure that any pressure created is released A 3 mL syringe with a 25 G needle was dropped through the septum. After complete addition of the oxyfluoride, gas chromatography analysis was performed. The differences observed in the reaction mixture due to the use of these different bases are shown in Table 1.

[0036]

[Table 1]

^* [3- (Perfluoro-2,5,8,11-tetramethyl-3,6,9,1
2-tetraoxapentadecanoyl) oxypropyl] heptamethylcyclotetrasiloxane vs. observed product (provided that perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoic acid Excluding those with retention).

Example 5 A 250 mL three-neck round bottom flask equipped with a magnetic stir bar, temperature probe and additional funnel was charged with 34.6 g of 99% (3-hydroxypropyl) heptamethylcyclotetrasiloxane (101 mmol) and 17.0 g of K ₂ HPO ₄ (97.6 mg equivalent) was charged.
The mixture was stirred and 87.6 g of hexafluoropropene oxide oligomeric acid fluoride (119 mmol) having an average degree of polymerization of 4.4 was added dropwise at such a rate that the temperature did not exceed 40 ° C. The contents of the pot were placed in a line in a funnel attached to a filter flask with a 1μ filter and collected in the flask when vacuum was applied to the flask. Transfer 100.6 g of the liquid in the filter to a 250 mL round bottom flask and distill at 51-128 ° C. and 0.05-0.25 mmHg to give 68 g (57% yield) of [3- (oligohexafluoro-peneoxy). Deoil) oxypropyl] heptamethylcyclotetrasiloxane (12.2 mmol) was obtained, which was of the formula (I)
m is 1, n is 3, X is OC (O), and the R ^F formula (II)
(Where p is 4.1), especially corresponding to that shown in formula (VII), where p is an average of 4.1.

The monodispersion from Examples 1 to 3 with a dispersion index X _w / X _n of 1.1 as determined by spectroscopy from ¹⁹ F NMR from the integral ratio of the CF ₃ signal and by gas chromatography. Assuming the relative response of individual homologs in proportion to their mass and retention time of individual homologs as determined from standards. The product was analyzed by spectroscopy with the following results: ¹ H NMR 400 MHz, CDCl ₃ : d 0.1 (s 21H), 0.6 (t 2H),
1.8 (p 2H), 4.4 (m 2H); ¹⁹ F NMR 376 MHz, CDCl ₃ : d -81 (CF ₃ ), -82 (CF ₃ ), -83 (CF ₃ ), -85 (CF ₃ ), -130 (CF ₂ ), -132 (CF ₂ ), -145 (CF); IR (N
Net liquid in aCl): cm ^-1 : 2970 (m), 1780 (s), 1245 (vs), 1200 (
s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).

Example 6 A 25 mL round bottom flask equipped with a magnetic stir bar and additional funnel was charged with 4.0 g of (3-
(Hydroxypropyl) heptamethylcyclotetrasiloxane (12 mmol) and 1
0.0 g of pyridine (13 mmol) was charged. The mixture was stirred and 5.0 g of perfluorooctanoyl chloride (12 mmol) was added dropwise. After complete addition of the oxyfluoride, gas chromatography analysis indicated that essentially all of the acid chloride and most of the cyclosiloxane had been consumed with the formation of one product as 96.5% of the mixture. The contents of the flask were filtered into a 50 mL one neck round bottom flask using a 0.45μ syringe filter. Wash the solid in the syringe with an additional 2.5 mL of pentane,
Filtered into L round bottom flask. The contents of the flask were distilled at 82 ° C. and 0.04 mmHg to give a fraction of 3- (perfluorooctanoyl) oxypropyl] heptamethylcyclotetrasiloxane, which had the formula (I) where m is 1 and n is 3
X is OC (O) and R ^F is a C7 perfluorinated linear monovalent alkyl group, or especially as shown in formula (VIII) below: Corresponding.

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Example 7 A 100 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 4.2 g of allyl alcohol (72 mmol) and 9.5 g of anhydrous pyridine (120 mmol).
The mixture was stirred and 40 g of 97% perfluoro-2,5,8-trimethyl-3,6,
9-Trioxadodecanoyl fluoride (60 mmol) was added dropwise. After complete addition of the oxyfluoride, two phases resulted. Stirring was stopped and the contents were poured into a separatory funnel. Gas chromatography analysis of the lower layer showed no oxyfluoride, indicating the formation of very small amounts of allyl alcohol and significant amounts of one product. The lowermost ester layer was removed, and the upper layer was 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 washed with another 20 mL portion of dilute hydrochloric acid and then twice with a 20 mL portion of water. The ester was transferred to a round bottom flask and distilled at 62-64 ° C. and 3 mm Hg to give 29.0 g (69% yield) of> 99% [3-perfluoro-2,
A fraction of (5,8-trimethyl-3,6,9-trioxadodecanoyl) oxy] -1-propene (41 mmol) was obtained.

A 25 mL three neck round bottom flask was equipped with a magnetic stir bar, condenser and temperature probe. The flask was charged with 10.0 g of> 99% [3-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl) oxy] -1-propene and 4.0 g
g of heptamethylcyclotetrasiloxane (14 mmol) were charged. 80 ° C the mixture
And 10 μL of Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via syringe. Increased temperature. Temperature is 90 ℃
Exothermic reaction occurred, causing the temperature to rise sharply to 105 ° C but immediately dropped to 100 ° C. After gas chromatography analysis showed a low conversion, the temperature was increased to 100 ° C. and another 5 μL of the platinum catalyst solution was added to the mixture, causing another exothermic reaction. The heating was then stopped and the gas chromatographed, and all reactions were completed with the desired product [3- (perfluoro-2,5,8-trimethyl-3,6.
, 9-Trioxadodecanoyl) oxypropyl] heptamethylcyclotetrasiloxane was consumed, which was shown to make up only 18% of the mixture.

Example 8 A 100 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 9.0 g of allylamine (160 mmol). The liquid is stirred and 40 g of 97% perfluoro-2
, 5,8-Trimethyl-3,6,9-trioxadodecanoyl fluoride (60 m
mol) was added dropwise. Dilute hydrochloric acid was added to the flask, the biphasic mixture was transferred to a separatory funnel and the aqueous layer was separated from the amide layer. The amide layer was washed again with dilute hydrochloric acid and twice with water. The amide layer was transferred to a round bottom flask and distilled at 101 ° C. and 3 mm Hg to give 21.6 g (52% yield) of> 99% N-allyl perfluoro-2,5,8-trimethyl-3,6,9 -A fraction of trioxadodecaneamide (31 mmol) was obtained.

A 25 mL three-neck round bottom flask was equipped with a magnetic stir bar, condenser and temperature probe. The flask was charged with 10.0 g of> 99% N-allylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecaneamide (14 mmol) and 4.0 g of heptamethylcyclotetrasiloxane (14 mmol). I put it in. The mixture was heated to 100 ° C. and 10 μL of Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via syringe. Exothermic reaction occurs, temperature is 147 ℃
But jumped 10 minutes later. Gas chromatography analysis indicated high conversion to a single product. Distill the contents of the flask at 0.020 mmHg at 116-20 ° C,
5.7 g (43% yield) of> 99% N- (3-heptamethylcyclotetrasiloxane-yl) propylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecaneamide (6 mmol) Although to obtain a fraction, which is the formula (I) (wherein, m is 1, n is 3, X is NHC (O), and R ^F is the formula (II) (wherein ,
p is 3) or in particular of the following formula (IX), wherein R = H and p =
3)).

Analysis of the product by spectroscopy gave the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (m 21H), 0.6 (t 2H), 1.7 (p 2H), 3.4 (m 2H), 6.7 (s 1H); IR
(Net liquid in NaCl): cm ^-1 : 3460 (m), 2970 (m), 1705 (s), 1550
(M), 1310 (m), 1245 (vs), 1200 (s), 1150 (s), 1070 (vs), 995 (s),
970 (s), 810 (vs), 750 (m).

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Example 9 A 100 mL round bottom flask equipped with a magnetic stir bar and an additional funnel was charged with 5.0 g of N-
Methylallylamine (70 mmol) was charged. The liquid was stirred and 17.5 g of 97% perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (26 mmol) was added dropwise. The reaction mixture was transferred to a separatory funnel and the amide layer was washed twice with dilute hydrochloric acid and once with water. The amide layer was transferred to a round bottom flask at 98 ° C and
Distillation at 2.4 mm Hg gave 14.3 g (77% yield) of> 99% N-allyl-N-methyl-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecaneamide (20 mmol). ) Was obtained.

A 25 mL three-neck round bottom flask was equipped with a magnetic stir bar, condenser and temperature probe. In a flask, 7.0 g of> 99% N-allyl-N-methylperfluoro-2,
5,8-trimethyl-3,6,9-trioxadodecanamide (10 mmol) and
2.8 g of heptamethylcyclotetrasiloxane (10 mmol) were charged. The mixture
Heat to 106 ° C. and add 10 μL of Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) via syringe. An exothermic reaction occurred, causing the temperature to spike to 155 ° C, but fell after 3 minutes. Gas chromatography analysis
High conversion to a single product was indicated. The contents of the flask were distilled at 0.05 mmHg at 100-500C to give 5.2 g (53% yield) of> 99% N- (3-heptamethylcyclotetrasiloxane-yl) propyl-N-methylperfluoro-2. , 5,8-Trimethyl-3
, 6,9-Trioxadodecanamide (5.2 mmol) was obtained, which was of the formula (
I) wherein m is 1, n is 3, X is N (CH ₃ ) C (O),
And R ^F is according to formula (II) (where p is 3) or in particular of formula (IX)
(Where R = CH ₃ and p = 3).

The product was analyzed by spectroscopy with the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (m 21H), 0.5 (m 2H), 1.7 (m 2H), 3.1 (m 3H), 3.5 (m 2H); IR
(Net liquid in NaCl): cm ^-1 : 2970 (m), 1685 (s), 1410 (w), 1300
(M), 1245 (vs), 1200 (s), 1140 (m), 1080 (vs), 995 (s), 970 (s),
810 (vs), 750 (m).

Example 10 In a 500 mL round bottom flask equipped with a magnetic stir bar, temperature probe, condenser and additional funnel, 11.0 g of allylamine (193 mmol) and 15 g of pyridine (190 mmol)
). The liquid was stirred and 150 g of hexafluoropropene oxide oligomeric acid fluoride (205 mmol) having an average degree of polymerization of 4.4 was added dropwise. The contents of the flask were transferred to a separatory funnel and washed twice with dilute hydrochloric acid and then twice with water. The amide layer was transferred to a round bottom flask. Distill the product at 95-190 ° C and 5.1 mmHg to give 125 g
A fraction of N-allyl oligohexafluoropropene-oxide-oilamide (84% yield) was obtained.

A 250 mL three-necked round bottom flask was equipped with a magnetic stir bar, condenser and temperature probe. The flask was charged with 5.0 g of N-allyl oligohexafluoropropene-oxide-oilamide (6.5 mmol) and 30 g of heptamethylcyclotetrasiloxane (106 mmol). The mixture was heated to 100 ° C. and 30 μL of Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) was added via syringe. An additional 70 g of N-allyl oligohexafluoropropene-oxide-oilamide (91 mmol) was added dropwise. After the addition of the allylamide is complete, an additional 5 μL of Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) in xylene
Was injected into the flask. The resulting liquid was transferred to a distillation flask and 78 g (69% yield) of 91% N- (3-heptamethylcyclotetrasiloxane-yl) propyl oligohexafluoropropene oxide-oilamide (91 mmol) was added. but obtained, which is the formula (I) (wherein, m is 1, n is 3, X is NHC (O), and R ^F is the formula (II) (wherein, p is 3.2 Or in particular of the formula (I
X) where R = H and p average 3.2.
Corresponding to

Individual homologs proportional to their mass and retention time of the homologs, as determined by gas chromatography, with a dispersion index X _w / X _n of 1.1, as determined from one dispersion standard from Example 8. Assume the relative response of the body. The main impurity in the product is unreacted N-
Allyl oligohexafluoropropene oxide-oil amide.

Example 11 1.0 g of 99% [3- (perfluoro-2,5,8,11-tetramethyl-3,
6,9,12-Tetraoxapentadecanoyl) oxypropyl] -heptamethylcyclotetrasiloxane (0.87 mmol) in a 1.5 dram vial containing 2.0
μL of trifluoromethanesulfonic acid (0.023 mmol) was injected and the mixture was shaken. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes to produce a slow flowing heavy oil when the vial was brought to room temperature. The oil was warmed again and left for 4 hours. Little or no change appeared in the oil. 0.01 g M in vial
gO (0.2 meq) was added and the oil was warmed using a heating gun to disperse the salt. After cooling the mixture, 1 mL of pentane was added to the vial and the mixture was shaken.
Upon standing, two liquid phases and a solid phase appeared. 3 mL with 0.45μ filter
The liquid layer was filtered from the solid phase using a syringe into a 3 dram vial. The 1.5 dram vial and syringe were rinsed with pentane, and the liquid was injected through a filter into a 3 dram vial to yield a perfluoroether siloxane mixture of about 20% by weight in pentane.

The two phases were dispersed by shaking, and immediately a 3 μL sample was drawn into a syringe and injected into the gas chromatograph. The signals were observed on chromatographic traces with four groups of signal patterns. The two groups with short retention times each showed four narrow, well-resolved signals that decreased in intensity with increasing retention time. Retention times for the first group were the same as for octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetradecamethylcycloheptasiloxane.

The largest peak in the second group is [3- (per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] heptamethylcyclo It had a retention time of tetrasiloxane. Since complete redistribution of siloxane units must occur during the polymerization, the molar ratio of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane is K ₄ / K ₄ : K ₅ (0.75) for a random arrangement of siloxane units. _{/ K 4: K 6 (0.75} ) 2 / K 4 equally there should, in this case, dimethylsiloxane units constitute 75% of the total siloxane units in the copolymer, the polymerization resulted in high molecular weight copolymer. Assuming a molar response factor for the homolog in the gas chromatographic trace that is proportional to the homolog molecular weight,
The observed molar ratio of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane of: 4: 1 was consistent with a theoretical ratio of 10: 4: 1.

The second group comprises [3- (per-fluoro-2,5,8,11-tetramethyl-3,
6,9,12-tetraoxapentadecane-oil) oxypropyl] heptamethylcyclotetrasiloxane, [3- (per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxa Pentadecane-oil) oxypropyl] nonamethylcyclopentasiloxane, [3- (per-fluoro-2,5
, 8,11-Tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] undecamethylcyclohexasiloxane and [3- (
Per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] tridecamethylcycloheptasiloxane.

[3- (Perfluoro-2,5,8,11-tetramethyl-3,6,9,1
2-tetraoxapentadecane-oil) oxypropyl] heptamethylcyclotetrasiloxane: [3- (per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecane-oil) Oxypropyl] nonamethylcyclopentasiloxane: [3- (per-fluoro-2,5,8,11
The molar ratio of -tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] undecamethylcyclohexasiloxane was observed to be 10: 5: 2 by gas chromatography trace, This is K ₄ / K ₄ : K ₅ (
0.75) / K ₄ : K ₆ (0.75) ² / K ₄ The theoretical ratio was consistent with 10: 5: 2. Matching of this ratio confirmed that complete and random redistribution had occurred and that high molecular weight copolymers had been formed.

The upper layer was withdrawn 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 was shaken. The upper layer was again removed via syringe and placed in a scintillation vial. Evaporation of the pentane from the solution in the scintillation vial at room temperature under a stream of nitrogen gave 0.2 g of an oil, which was indistinguishable from the original dispersion by gas chromatography trace, except for [3- ( Per-fluoro-2,5
Compared to the peak for 8,11-tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] heptamethylcyclotetrasiloxane, there is little signal from pentane and octamethylcyclotetrasiloxane and The signal for decamethylcyclopentasiloxane was significantly reduced and the signal for dodecamethylcyclohexasiloxane was slightly reduced.

A lower gas chromatographic trace in a 3 dram vial showed little signal from the equilibrium cyclosiloxane. The pentane expanding the copolymer was removed by heating the vial on a hot plate while passing a stream of nitrogen across the surface. This resulted in 0.6 g of rubber, which showed no flow on cooling when the vial was left for 2 weeks, indicating that the molecular weight of the copolymer was high.

Example 12 1.0 g of> 99% N- (3-heptamethylcyclotetrasiloxane-yl) propyl-N-methylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide In a 1.5 dram vial containing (0.87 mmol), 2.0 μL of trifluoromethanesulfonic acid (0.023 mmol) was injected and the mixture was shaken. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes to produce a slow flowing heavy oil when the vial was brought to room temperature. The oil was warmed again and left for 4 hours. The resulting viscous linear-cyclic mixture was 99% [3- (perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl) oxy) of Example 11. Propyl] -heptamethylcyclotetrasiloxane.

Example 13 1.0 g of> 99% N- (3-heptamethylcyclotetrasiloxane-yl) propylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecaneamide (0.87 mmol) 2.0 μL of trifluoromethanesulfonic acid (0.023 mmol) was injected into a 1.5 dram vial containing and the mixture was shaken. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes so that when the vial was returned to room temperature, a heavy oil with little flow appeared. The oil was warmed again and left for 4 hours. The resulting viscous linear-cyclic mixture was 99% [3- (perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl) oxy) of Example 11. [Propyl] -heptamethylcyclotetrasiloxane was more viscous than the mixture resulting from the polymerization.

Example 14 3.0 μL in a 1.5 dram vial containing 2.0 g of [3- (oligohexafluoro-peneoxydeoyl) oxypropyl] heptamethylcyclotetrasiloxane (1.7 mmol) from Example 5 Trifluoromethanesulfonic acid (0.035 mmol
) Was injected and the mixture was shaken. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes to produce a slow flowing heavy oil when the vial was brought to room temperature. The oil was warmed again and left for 4 hours. To the mixture, 0.021 MgO (0.52 mmol)
Was added and the mixture was warmed with a heating gun to assist in mixing the powder. Example 11
99% [3- (perfluoro-2,5,8,11-tetramethyl-3,6,9,1
2-tetraoxapentadecanoyl) oxypropyl] -heptamethylcyclotetrasiloxane, a viscous linear-cyclic mixture practically similar to that resulting from polymerization,
Observed by gas chromatography analysis.

Example 15 2.0 g of N- (3-heptamethylcyclotetrasiloxane-from Example 10
Yl) propyl oligohexafluoropropene oxide-oilamide (1.7 mm
ol) into a 1.5 dram vial, 3.0 μL of trifluoromethanesulfonic acid (0.035 mmol) was injected and the mixture was shaken. Warm the vial with a heating gun,
The viscosity was increased for 10 minutes such that the heavy oil showed almost no flow when the vial was returned to room temperature. The oil was re-warmed and left for 24 hours. The mixture became cloudy at room temperature, but became clear on warming. To the mixture was added 0.012 MgO (0.30 mmol) and the mixture was warmed with a heating gun to assist in mixing the powder. Example 11-99
% [3- (perfluoro-2,5,8,11-tetramethyl-3,6,9,12
-Tetraoxapentadecanoyl) oxypropyl] -a heptamethylcyclotetrasiloxane linear-cyclic mixture, which was practically similar to that resulting from polymerization, was observed by gas chromatography analysis.

Example 16 2.0 g of N- (3-heptamethylcyclotetrasiloxane-from Example 10
Yl) propyl oligohexafluoropropene oxide-oilamide (1.7 mm
ol) in a 1.5 dram vial, 19.0 μL of tetrabutylammonium fluoride (0.019 mmol) in tetrahydrofuran was injected and the mixture was shaken. The vial was gradually warmed with a heating gun for 10 minutes. After cooling to room temperature, a viscous mixture was observed. The heating of the vial was repeated six times, until a heavy oil showing a very slow flow occurred when the vial was returned to room temperature. Upon heating, no apparent increase in viscosity was observed. The oil was re-warmed and left for 24 hours. The mixture remained clear at room temperature. The vial was then rapidly warmed, producing foam, probably due to the decomposition of the tetrabutylammonium salt with the release of tributylamine and butene. A linear-cyclic mixture practically similar to that produced in Example 15 was observed by gas chromatography analysis.

Example 17 A 50 mL three-necked round bottom flask was equipped with a magnetic stir bar, condenser and temperature probe. The flask is charged with 10.0 g of 1H, 1H, 2H-perfluoro-1-octene (
28.9 mmol) and 10.0 g of heptamethylcyclotetrasiloxane (35.4 mmol)
Was introduced. The mixture was heated to 90 ° C. and 5 μL of Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via syringe. An exothermic reaction occurred, causing the temperature to rise to 130 ° C., but fell after 3 minutes. Gas chromatography analysis showed low conversion to a single product. Addition of 20 μL of Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) did not result in higher conversion. Distill the contents of the flask at <2 mmHg at 80 ° C. to give 4.2 g (23% yield)
(6.7 mmol) was obtained according to the formula (I) (where m is 1 and n is 1).
X is CH ₂ , and R ^F is a C 6 perfluorinated linear monovalent alkyl group, or especially as shown in formula (X) below, wherein q = 5 Corresponding).

The product was analyzed by spectroscopy with the following results: ¹ H NMR 400 MHz, CD
Cl ₃ : d 0.1 (m 21H), 0.8 (m 2H), 2.1 (m 2H); IR (net liquid in 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 (vs).

[0066]

Embedded image

Example 18 1.5 g of 1H, 1H, 2H, 2H, 1- (heptamethylcyclotetrasiloxane-yl) perfluorooctane (3.2 mmol) from Example 17
In a dram vial, 3.0 μL of trifluoromethanesulfonic acid (0.035 mmol) was injected and the mixture was shaken. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes so that the vial returned to room temperature resulting in a rubber that showed little flow. The rubber was warmed again and left for 24 hours. The vial contains 0.021 MgO (0.5
2 mmol) was added and the mixture was warmed with a heating gun to aid in the dispersion of the powder. 99% of Example 11 [3- (perfluoro-2,5,8,11-tetramethyl-3,6
, 9,12-Tetraoxapentadecanoyl) oxypropyl] -heptamethylcyclotetrasiloxane, a linear-cyclic mixture practically similar to that resulting from polymerization, was observed by gas chromatography analysis.

Example 19 0.20 g of 99% [3- (perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl) oxypropyl] from Example 2 -Into a 1.5 dram vial containing heptamethylcyclotetrasiloxane (0.18 mmol) and 9.5 g octamethylcyclotetrasiloxane (32.0 mmol), inject 15 [mu] L trifluoromethanesulfonic acid (0.17 mmol) and dispense the mixture. Shake. The vial was warmed with a heating gun and the viscosity was increased for 10 minutes so that the vial returned to room temperature resulting in a rubber that showed little flow. The rubber was warmed again and left for 24 hours. 0.01 g MgO (0.2 mmol) was added to the vial and the mixture was warmed using a heating gun to aid in powder dispersion. The resulting line-
The cyclic mixture was observed by gas chromatography analysis.

Since complete redistribution of the siloxane units must occur during the polymerization, the molar ratio of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane: dodecamethylcyclohexasiloxane is such that K _{4 with} respect to the random arrangement of the siloxane units /
K ₄ : K ₅ (0.997) / K ₄ : K ₆ (0.997) ² / K ₄ should be equal, in this case
Dimethylsiloxane units make up 99.7% of the total siloxane units in the copolymer,
The polymerization resulted in a high molecular weight copolymer.

Assuming a molar response factor for the homolog in the gas chromatographic trace that is proportional to the molecular weight of the homolog, the observation of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane: dodecamethylcyclohexasiloxane of 10: 5.1: 1.3 The molar ratio obtained was in good agreement with the theoretical ratio of 10: 5.2: 1.8. Octamethylcyclotetrasiloxane: molar ratio of [3- (per-fluoro-2,6,8,11-tetramethyl-3,6,9,12-tetraoxapentadecane-oil) oxypropyl] heptamethylcyclotetrasiloxane Is determined to be 100: 2, which is
Relations random polymerization to high molecular weight ^{_{K 4 (0.997) 4 / 4K}} 4 (0.997) 3 /(0.00
Good agreement with the theoretical ratio of 100: 1.2 from 3).

Example 20 0.20 g of 99% [3- (perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxapentadecanoyl) oxypropyl]
1.5 containing heptamethylcyclotetrasiloxane (0.17 mmol), 1.90 g of octamethylcyclotetrasiloxane (6.4 mmol) and 0.020 g of 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane (0.006 mmol) dram
Into the vial, 3 μL of trifluoromethanesulfonic acid (0.03 mmol) was injected and the mixture was shaken. The vial was gradually warmed with a heating gun to increase viscosity for 30 minutes. The mixture was re-warmed and left for 24 hours. Add 0.02 g of MgO (0.4
mmol) was added and the mixture was warmed using a heating gun to aid in powder dispersion.
The resulting linear-cyclic mixture was dissolved in 6 mL of cyclohexane and analyzed by gas chromatography.

Since complete redistribution of the siloxane units must occur during the polymerization, the molar ratio of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane: dodecamethylcyclohexasiloxane is such that K _{4 with} respect to the random arrangement of the siloxane units /
K ₄ : K ₅ (0.993) / K ₄ : K ₆ (0.993) ² / −K ₄ should be equal, where the dimethylsiloxane units make up 99.3% of the total siloxane units in the copolymer and the polymerization is A high molecular weight copolymer resulted. Assuming a molar response factor for the homologue in the gas chromatographic trace that is proportional to the molecular weight of the homologue, octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane of 10: 5.5: 1.7:
The observed molar ratio of dodecamethylcyclohexasiloxane was in good agreement with the theoretical ratio of 10: 5.2: 1.8. A small peak was observed in the gas chromatographic trace, which had a retention time for vinyl heptamethylcyclotetrasiloxane and vinylnonamethylcyclopentasiloxane, which was higher than 1,3,5,7-
2 shows that methylvinylsiloxane units from tetravinyltetramethylcyclotetrasiloxane were randomly dispersed throughout the copolymer and cyclic oligomer.

Example 21 0.15 g of 94% [3- (perfluoro-2,5-dimethyl-3,6-dioxanonane-oil) oxypropyl] -heptamethylcyclotetrasiloxane (0.17 g
mmol), 2.15 g of octamethylcyclotetrasiloxane (7.2 mmol) and 0.0
33 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (0.15 m
mol) was injected into a 1.5 dram vial, 3 μL of trifluoromethanesulfonic acid (0.03 mmol) was injected and the mixture was shaken. Warm the vial with a heating gun,
The viscosity was increased for 10 minutes. 0.05 g MgO (1 mmol) was added to the vial. The copolymer-cyclic mixture was dissolved in 3 mL of cyclohexane and analyzed by gas chromatography.

Since the complete redistribution of siloxane units must occur during the polymerization, the molar ratio of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane: dodecamethylcyclohexasiloxane is such that the random ratio of siloxane units is K ₄ /
K ₄ : K ₅ (0.994) / K ₄ : K ₆ (0.994) ² / K ₄ should be equal, in this case
Dimethylsiloxane units make up 99.4% of the total siloxane units in the copolymer,
Polymerization resulted in a high molecular weight copolymer because the polymer with a degree of polymerization of about 200 was targeted by the ratio of cyclosiloxane to disiloxane used. Assuming a molar response factor for the homologue in the gas chromatographic trace that is proportional to the molecular weight of the homologue, the observed moles of octamethylcyclotetrasiloxane: decamethylcyclopentasiloxane: dodecamethylcyclohexasiloxane of 10: 6.4: 2.1 The ratio agreed well with the theoretical ratio of 10: 5.2: 1.8. Unreacted 1,3-divinyl-1,
1,3,3-tetramethyldisiloxane was not observed in the gas chromatographic trace.

The present invention may be embodied in other specific forms without departing from the spirit of its essential attributes, and therefore, when indicating the scope of the present invention, the appended claims will not be taken from the foregoing description. Reference should be made to The patents and publications referred to above are incorporated herein by reference.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY , CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor Shafar, John Scott. 32259, Florida, United States, Fruits Cove, Kalmia Court 1112 F-term (reference) 4H049 VN01 VP04 VQ11 VQ79 VQ87 VR23 VR41 VU20 VW02 4J035 BA02 CA072 CA102 CA16N CA161 CA182 EA01 EB02 LA05

Claims (40)

[Claims] 1. A polymerizable cyclosiloxane having a monosubstituent containing a perfluorinated organic moiety, which is represented by the general formula (I): (Wherein m is an integer of 1 to 12; n is an integer of 1 to 4; X is O, NH, N (CH ₃ ), OC (O), NHC (O), N (CH ₃ )
Is a divalent radical selected from the group consisting of C (O) and CH _2, and R ^F is, or is perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F is a compound represented by the general formula (II): (Wherein p is an integer from 1 to 10). 2. The polymerizable cyclosiloxane according to claim 1, wherein m is 1 or 2. 3. The polymerizable cyclosiloxane according to claim 2, wherein n is 3 and X is OC (O). 4. The polymerizable cyclosiloxane according to claim 3, wherein R ^F is a perfluorinated ether group of the general formula (II), wherein p is 1 to 5. 5. The polymerizable cyclosiloxane according to claim 3, wherein R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms. 6. The polymerizable cyclosiloxane according to claim 2, wherein n is 3 and X is NHC (O). 7. The polymerizable cyclosiloxane according to claim 6, wherein R ^F is a perfluorinated ether group of the general formula (II), wherein p is 1 to 5. 8. The polymerizable cyclosiloxane according to claim 6, wherein R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms. 9. The polymerizable cyclosiloxane according to claim 2, wherein n is 3 and X is N (CH ₃ ) C (O). 10. The polymerizable cyclosiloxane according to claim 9, wherein R ^F is a perfluorinated ether group of the general formula (II), wherein p is 1 to 5. 11. The polymerizable cyclosiloxane according to claim 9, wherein R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms. 12. The polymerizable cyclosiloxane according to claim ₂ , wherein n is 1 and X is CH ₂ . 13. The polymerizable cyclosiloxane according to claim 12, wherein R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms. 14. The polymerizable cyclosiloxane according to claim 12, wherein R ^F is a perfluorinated ether group of the general formula (II), wherein p is 1 to 5. 15. A general formula: (Wherein, m is independently an integer from 1 to 12, n is each independently an integer from 1 to 4, and X is each independently O, NH, N (CH ₃ ), OC (O), NHC (O), N (
CH ₃ ) a divalent group selected from the group consisting of C (O) or CH ₂ , wherein R ^F is each independently a perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms; Or the general formula (II): (Where p is an integer from 1 to 10) and q is from 2 to about 1,000,000. 16. The copolymer of claim 15, prepared by ring-opening polymerization of a monosubstituted polymerizable cyclosiloxane containing a perfluorinated organic moiety, wherein said cyclosiloxane has the general formula (I) : (Wherein m is an integer of 1 to 12; n is an integer of 1 to 4; X is O, NH, N (CH ₃ ), OC (O), NHC (O), N (CH ₃ )
Is a divalent radical selected from the group consisting of C (O) and CH _2, and R ^F is, or is perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F is represented by the general formula (II): Wherein p is an integer from 1 to 10 is a perfluorinated ether group. 17. A copolymer prepared by ring-opening polymerization of a polymerizable cyclosiloxane according to claim 16, wherein n is 3, X is OC (O), and R ^F has the general formula (II) ) Wherein p is 1-5, wherein the copolymer is a perfluorinated ether group. 18. A copolymer prepared by ring-opening polymerization of a polymerizable cyclosiloxane according to claim 16, wherein n is 3, X is OC (O), and R ^F has 2 to 2 carbon atoms. A copolymer that is 10 perfluorinated linear alkyl groups. 19. A copolymer prepared by ring-opening polymerization of a polymerizable cyclosiloxane according to claim 16, wherein n is 3, X is NHC (O), and R ^F has the general formula (II) ) Wherein p is 1-5, wherein the copolymer is a perfluorinated ether group. 20. A copolymer prepared by ring-opening polymerization of the polymerizable cyclosiloxane of claim 16, wherein n is 3, X is NHC (O), and R ^F has 2 to 2 carbon atoms. A copolymer which is 10 perfluorinated linear alkyl groups. 21. A copolymer prepared by ring opening polymerization of the polymerizable cyclosiloxane of claim 16, wherein n is 3, X is N (CH ₃ ) C (O), and R ^F Is a perfluorinated ether group of the general formula (II) wherein p is 1-5. 22. A copolymer prepared by ring-opening polymerization of the polymerizable cyclosiloxane of claim 16, wherein n is 3, X is N (CH ₃ ) C (O), and R ^F Is a perfluorinated linear alkyl group having 2 to 10 carbon atoms. 23. A copolymer prepared by ring-opening polymerization of the polymerizable cyclosiloxane of claim 16, wherein n is 1, X is CH ₂ , and R ^F has from 2 to 10 carbon atoms. Copolymers that are perfluorinated linear alkyl groups. 24. A copolymer prepared by ring-opening polymerization of the polymerizable cyclosiloxane of claim 16, wherein n is 1, X is CH ₂ , and R ^F is of the general formula (II) ( Wherein p is from 1 to 5). 25. A polymerizable cyclosiloxane having a monosubstituent containing a perfluorinated organic moiety and having the general formula (I): 25 (Wherein m is an integer of 1 to 12; n is an integer of 1 to 4; X is O, NH, N (CH ₃ ), OC (O), NHC (O), N (CH ₃ )
Is a divalent radical selected from the group consisting of C (O) and CH _2, and R ^F is, or is perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F is a compound represented by the general formula (II): (Wherein p is an integer from 1 to 10) a perfluorinated ether group, and (b) selected from the group consisting of cyclodimethylsiloxane, polydimethylsiloxane, and mixtures thereof. Copolymers wherein the copolymer is prepared by copolymerization of a substituent containing a lower proportion of fluorinated siloxane groups than the cyclosiloxane of formula (I). 26. (a) n is 3, X is OC (O), and R ^F
Is a perfluorinated ether group of the general formula (II) wherein p is 1 to 5, and (b) ring opening of octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane 3. A composition prepared by polymerization.
5. The copolymer according to 5. 27. (a) n is 3, X is OC (O), and R ^F
Is prepared by ring-opening polymerization of said polymerizable cyclosiloxane, which is a perfluorinated linear alkyl group having 2 to 10 carbon atoms, and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane. Copolymer. 28. (a) n is 3, X is NHC (O) and R ^F Is a perfluorinated ether group of the general formula (II) (wherein p is 1 to 5)
The polymerizable cyclosiloxane, and (b) octamethylcyclotetrasiloxa
Prepared by ring-opening polymerization of dimethyl or decamethylcyclopentasiloxane.
25. The copolymer according to 25. 29. (a) n is 3, X is NHC (O), and R ^F Is a perfluorinated linear alkyl group having 2 to 10 carbon atoms,
And (b) octamethylcyclotetrasiloxane or decamethylcyclope
26. The copolymer of claim 25 prepared by ring opening polymerization of a siloxane. 30. (a) n is 3, X is N (CH ₃ ) C (O),
And the polymerizable cyclosiloxane wherein R ^F is a perfluorinated ether group of the general formula (II) (where p is 1 to 5); and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane 26. The copolymer of claim 25 prepared by ring opening polymerization of 31. (a) n is 3, X is N (CH ₃ ) C (O),
And the ring-opening polymerization of the polymerizable cyclosiloxane wherein R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms, and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane. 25. The copolymer according to 25. 32. (a) said polymerizable cyclosiloxane, wherein n is 1, X is CH ₂ , and R ^F is a perfluorinated linear alkyl group having 2 to 10 carbon atoms; and (b) 26. The copolymer of claim 25 prepared by ring opening polymerization of octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane. 33. (a) wherein n is X is CH ₂ , and R ^F is a perfluorinated ether group of the general formula (II) wherein p is 1-5. 26. The copolymer of claim 25 prepared by ring opening polymerization of a polymerizable cyclosiloxane and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane. 34. The copolymer as defined above, wherein the copolymer comprises methyl hydrogensiloxy, methylvinylsiloxy, methylphenylsiloxy, methylcyanoethylsiloxy, hydroxypropylsiloxy, aminopropylmethylsiloxy, trifluoropropylmethylsiloxy, a mixture of any of the foregoing, and the like. 16. The copolymer of claim 15, further comprising other selected siloxy repeat units. 35. The copolymer as claimed in claim 30, wherein the copolymer comprises methyl hydrogen siloxy, methyl vinyl siloxy, methyl phenyl siloxy, methyl cyanoethyl siloxy, hydroxypropyl siloxy, aminopropyl methyl siloxy, trifluoropropyl methyl siloxy, a mixture of any of the foregoing, and the like. 26. The copolymer of claim 25 further comprising other selected siloxy repeat units. 36. The copolymer at both ends, wherein the polymerization equilibrates the cyclosiloxane with an endcapping agent selected from the group of disiloxanes, disiloxane equivalents incorporated in small polysiloxanes, and mixtures thereof. 17. The copolymer of claim 16, which is controlled by capping. 37. The copolymer at both ends, wherein the polymerization equilibrates the cyclosiloxane with an endcapping agent selected from the group of disiloxanes, disiloxane equivalents incorporated in small polysiloxanes and mixtures thereof. 26. The copolymer of claim 25, which is controlled by capping. 38. The copolymer at both ends, wherein the polymerization equilibrates the cyclosiloxane with an endcapping agent selected from the group of disiloxanes, disiloxane equivalents incorporated in small polysiloxanes and mixtures thereof. 35. The copolymer of claim 34, which is controlled by capping. 39. The copolymer at both ends, wherein the polymerization equilibrates the cyclosiloxane with an endcapping agent selected from the group of disiloxanes, disiloxane equivalents incorporated in small polysiloxanes and mixtures thereof. 36. The copolymer of claim 35, which is controlled by capping. 40. The formula (V): (Where n is an integer of 1 to 4, X is O, NH, N (CH ₃ ), OC (O), NHC (O), N (CH ₃ )
Is a divalent radical selected from the group consisting of C (O) and CH _2, and R ^F is, or is perfluorinated linear or branched monovalent alkyl group having 1 to 25 carbon atoms, or R ^F is a compound represented by the general formula (II): Wherein p is an integer from 1 to 10; r is 1 to t; s is tr; and t is 4 to 20. Siloxane.