Novel Fluorinated Glycidyl Ethers and Method of Making Them

Europa,schesP_ MM M M M Ml M I II II II Ml II I II J European Patent Office _ © Publication number: 0 527 020 B1 Office europeen des brevets

@ Date of filing: 31.07.92

® Priority: 31.07.91 JP 214670/92 @ Inventor: Takago, Toshio 31.07.91 JP 214672/91 No 94-7, Yanase 31.07.91 JP 214671/91 Annaka-shi, Gunma-ken (JP) @ Date of publication of application: Inventor: Inomata, Hlroshi 10.02.93 Bulletin 93/06 Shlnsakuragaoka Apt., No 11-20, Isobe 3-chome © Publication of the grant of the patent: Annaka-shl, 12.04.95 Bulletin 95/15 Gunma-ken (JP) Inventor: Taruml, Yasuo © Designated Contracting States: 224-17, Kenzakl-machl DE FR GB Takasakl-shl, Gunma-ken (JP) © References cited: Inventor: Yamaguchl, Hlromasa FR-A- 1 570 174 B205, Shlnpu Ryo, US-A- 2 839 514 No 1610, Nlshlkamllsobe US-A- 3 414 549 Annaka-shl, US-A- 3 504 000 Gunma-ken (JP) Inventor: Fukuda, Kenlchl CHEMICAL ABSTRACTS, vol. 67, no. 4, 24 No 1044-1, Shlmonojo-machl July 1967, Columbus, Ohio, US; abstract no. Takasakl-shl, 12045q, K.E. KOLB ET AL. 'Glass-sllane-ep- Gunma-ken (JP) oxy system." page 1162 ; 00 o © Proprietor: SHIN-ETSU CHEMICAL CO., LTD. CM 6-1, Ohtemachl 2-chome Chlyoda-ku Tokyo (JP) CM Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3. 10/3.09/3.3.3) EP 0 527 020 B1

0 Representative: Stoner, Gerard Patrick et al MEWBURN ELLIS York House 23 Klngsway London WC2B 6HP (GB)

2 EP 0 527 020 B1

Description

This invention relates to novel fluorinated glycidyl ethers including fluorinated unsaturated glycidyl ethers and silicon-modified fluorinated glycidyl ethers and methods for preparing the same. 5 One prior art well-known ether compound having a vinyl group and an oxirane ring in its molecule is allyl glycidyl ether of the following formula (see Beilstein, Third and Fourth Ed., Vol. 17, page 990).

CH2=CH - CH2 - O - CH2 - CH - CH2 \ / O

Because of its reactivity, this allyl glycidyl ether has been widely used in the industrial field as a monomer 75 for the preparation of a homopolymer or a copolymer with a compound having a carbon-to-carbon double bond, an intermediate reactant intended for silane coupling agents along with various silanes, a crosslinking agent for epoxy resins, and an intermediate reactant for forming resin monomers. Shokal et al. (1958 US-A-2839514) describe a process in which an unfluorinated allyl glycidyl ether is used to form a copolymer with styrene by the formation of carbon-to-carbon bonds. 20 Polymers and other products resulting from allyl glycidyl ether are low in water repellency, moisture resistance and compatibility with fluorinated materials. There is a need for imparting or improving such properties. Also known in the prior art are epoxy-modified silanes of the following formula:

25 XnR3.nSiCH2CH2CH2OCH2CH - CH2

30 wherein X is a hydrolysable group, R is a monovalent organic group, and n is an integer of 1 to 3. These compounds contain a X-Si group reactive with glass, metal, silica, quartz sand, etc. and an epoxy group reactive with an alcohol, amino or carboxyl group of organic resins in the same molecule so that they are very effective in increasing the mechanical strength and electrical properties of epoxy resin/glass laminates, 35 phenolic resin/glass laminates and phenolic resin shell molds. Such a compound was synthesised by Kolb et al. (1967 Chemical Abstracts, Vol. 67 No. 4, abstract 12045q. Treatment of silica with these compounds can modify the silica surface with an epoxy group-containing residue. However, these epoxy-modified silanes sometimes fail to provide sufficient water resistance and 40 heat resistance, and leave the possibility of decomposition of an ether linkage in their molecule. Pittman et al. (1970 US-A-3504000) have synthesised fluorinated glycidyl ethers and demonstrated their use, in both monomeric and polymeric forms, in imparting water and oil-repellency to textiles. However, the compatibility with fluorinated materials was not apparent, the polymers made were all oxygen-linked through the glycidyl oxygen and their combination with silicon was not disclosed. 45 The present invention provides a novel fluorinated unsaturated glycidyl ether which when products such as a homopolymer, copolymer of carbon-functional silane (e.g. silane coupling agent) are prepared therefrom, imparts or improves physical properties such as water repellency, moisture resistance and compatibility with other fluorinated materials which have never been available with products derived from allyl glycidyl ether. 50 In a second aspect, the present invention provides a method for preparing such a fluorinated unsaturated glycidyl ether. In a third aspect, the present invention provides a silicon-modified fluorinated glycidyl ether which is effective in improving the strength and electrical properties of laminates based on epoxy resins and phenolic resins and in modifying the surface of silica fillers and which when used in such application, can 55 impart fluorinated compounds' inherent properties such as water resistance, heat resistance and low surface energy to resins and fillers. In a fourth aspect, the present invention provides a method for preparing such a silicon-modified fluorinated glycidyl ether.

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The inventors have found that as shown by the following scheme A, by reacting a compound of the following formula (3) (that is, 1 ,1 ,1-trifluoro-2-trifluoromethyl-3-buten-2-ol or 1 ,1 ,1-trifluoro-2-trifluoromethyl-4- penten-2-ol) with chloromethyloxirane in the presence of at least one onium salt selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts in a two phase system of a basic aqueous phase and an organic phase, there is obtained a novel fluorinated unsaturated glycidyl ether of the following formula (1) having a trifluoromethyl group incorporated therein. This fluorinated unsaturated glycidyl ether is a useful monomer for the preparation of a homopolymer and copolymers with compounds having a carbon-to-carbon double bond, as well as a useful reactant for the preparation of carbon functional silanes and other products. 70 Reaction scheme A:

CH2=CH - (CH2)n - C - OH + C1CH2CH - CH /\ \ / 15 F3C CF3 0 (3)

NaOH aqueous solution > CH2=CH - (CH2)m - C - 0 - CH2 - CH - CH2 20 phase transfer catalyst /\ \ / F3C CF3 0 m = 0 or 1 (1)

25 The fluorinated unsaturated glycidyl ether of formula (1) according to the present invention can be used as a reactant for the preparation of various products by taking advantage of its reactivity since it contains a vinyl group and oxirane ring, both reactive, at its molecular ends like allyl glycidyl ether. For example, a homopolymer is obtained when the present compound is polymerised alone. Copolymers are obtained 30 when it is polymerized with other compounds having a carbon-to-carbon double bond or vinyl monomers. Carbon functional silanes such as silane coupling agents are obtained when various silanes are reacted to the present compound. Since the fluorinated unsaturated glycidyl ether according to the present invention contains trifluoromethyl groups in a molecule in addition to a vinyl group and oxirane ring, it can impart to the above-mentioned products novel physical properties such as water and oil repellency, low surface 35 tension, heat resistance, low refractive index, moisture resistance and compatibility with other fluorinated materials which have never been available with products derived from allyl glycidyl ether, that is, achieve significant improvements in such properties over the allyl glycidyl ether-derived products. Accordingly, the present compound is capable of imparting and/or improving these physical properties and can be utilized in deriving various other fluorinated compounds therefrom. Because of the inclusion of an oxirane ring, the 40 fluorinated unsaturated glycidyl ether of the present invention is also useful as a curing agent for epoxy resin and an intermediate reactant for various resin monomers. Also the inventors have found that as shown by the following reaction scheme B, by starting with the compound of formula (1), a novel fluorinated organic silicon compound or silicon-modified glycidyl ether of the following formula (2) is obtained. Since this novel fluorinated organic silicon compound of formula (2) 45 contains a X-Si group and an epoxy group in the same molecule like the prior art epoxy-modified silanes, it is effective for reinforcing the bond of epoxy and phenolic resins to inorganic materials such as glass, silica, metal, and quartz sand, contributes to improvements in mechanical strength and electrical properties of such composite materials. In addition, the CF3 groups in the molecule are effective in further improving water resistance and heat resistance. By treating silica with the compound of formula (2), the silica can be 50 not only modified on the surface with an epoxy-functional residue, but also improved in water resistance by virtue of CF3 groups, thus imparting affinity to fluororesins and fluororubbers. Moreover, since the compound of formula (2) according to the present invention contains two CF3 groups on the carbon at alpha-position of the ether bond, the ether bond is shielded so that the tendency of decomposition at this site is retarded. 55

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Reaction scheme B:

CH:-CH - (CH2)m - C - 0 - CH2 - CH - CH2 + XnR3_nSiH F3C CF3 0 (1) catalyst > 10 XnR3_nSi - CH2 - CH2 - (CH2), - C - 0 - CH2 - CH - CH2 /\ \ / F3C CF3 0 (2)

75 Catalyst: a transition metal, salt or complex thereof X: a hydrolyzable group R: a monovalent organic group n: an integer of 1 to 3 20 m: 0 or 1 Consequently, the present invention provides fluorinated glycidyl ethers of formula (1) and (2) and methods for preparing the same. FIG. 1 is an IR absorption spectrum of the fluorinated glycidyl ether prepared in Example 1. FIG. 2 is an IR absorption spectrum of the fluorinated glycidyl ether prepared in Example 3. 25 The fluorinated glycidyl ether in a first form of the present invention is a fluorinated unsaturated glycidyl ether of the following formula (1).

CH2=CH - ( CH2 ), - C - 0 - CH2 - CH - CH2 ... ( 1 ) 30 F3C CF3 0

Letter m is equal to 0 or 1. Included in formula (1) are a compound of formula (1a) wherein m = 0 and a 35 compound of formula (1b) wherein m = 1.

CH2=CHCOCH2CH - CH2 ... ( la ) 0 40 F3C CF3

CH2=CHCH2COCH2CH - CH2 ...(lb)

F3C CF3 O 45

The fluorinated unsaturated glycidyl ethers of formula (1) according to the present invention are novel useful compounds in that when products such as a homopolymer copolymer or carbon functional silane are 50 prepared therefrom, they can impart to the products physical properties such as water repellency, moisture resistance and compatibility with other fluorinated materials which have never been available with the prior art allyl glycidyl ether-derived products. They are also useful as cross linking agents for epoxy resins and intermediate reactants for forming various resin monomers.

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The compounds of formula (1) can be prepared by reacting compounds of the following formula (3):

CH2=CH - (CH2)„ - C - OH •-• (3) /\ - F3C CF3

wherein m is equal to 0 or 1 with chloromethyloxirane in the presence of at least one onium salt selected 10 from the group consisting of quaternary ammonium salts and quaternary phosphonium salts in a two phase system of a basic aqueous phase and an organic phase. Among the compounds of formula (3) which are one of the starting reactants used in this method, one compound of formula (3) wherein m = 0 is a known compound designated 1 ,1 ,1 -trifluoro-2-trifluoromethyl- 3-buten-2-ol and may be readily prepared by reacting vinyl magnesium bromide with hexafluoroacetone, for 15 example. The other compound of formula (3) wherein m = 1 is also a known compound designated 1,1,1- trifluoro-2-trifluoromethyl-4-penten-2-ol and may be readily prepared by reacting propene with hexafluoroacetone, for example. Another starting reactant is chloromethyloxirane which is a known compound and may be readily prepared in a conventional manner. 20 For reaction, the compound of formula (3) and chloromethyloxirane are generally used in a molar ratio of from about 1:1 to about 1:50, preferably from about 1:2 to about 1:10. The basic aqueous phase used in the method may be selected from aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and aqueous solutions of alkaline earth metal hydroxides such as calcium hydroxide, with aqueous solutions of sodium hydroxide, potassium 25 hydroxide and calcium hydroxide being preferred. The basic aqueous solution generally has a concentration of from about 5% by weight to saturation, preferably from about 10 to 30% by weight. The amount of the base used may be selected in the range of about 0.1 to 10 equivalents, preferably about 0.5 to 2 equivalents relative to the compound of formula (3). In the method of the present invention, an onium salt selected from the group consisting of quaternary 30 ammonium salts and quaternary phosphonium salts is used as a phase transfer catalyst. The quaternary ammonium salts are salts of quaternary ammonium ions with anions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n- butylammonium ion, tri-n-octylmethylammonium ion, cetyltrimethylammonium ion, benzyltrimethylam- monium ion, benzyltriethylammonium ion, cetylbenzyldimethylammonium ion, cetylpyridinium ion, n- 35 dodecylpyridinium ion, phenyltrimethylammonium ion, phenyltriethylammonium ion, N-benzylpicolinium ion, pentamethonium ion, hexamethonium ion, etc. Examples of the anion include chloride ion, bromide ion, fluoride ion, iodide ion, hydrogen sulfate ion, sulfate ion, phosphate ion, nitrate ion, hydroxy ion, acetate ion, benzoate ion, benzenesulfonate ion, p-toluenesulfonate ion, etc. The quaternary phosphonium salts are salts of quaternary phosphonium ions with anions. Examples of 40 the quaternary phosphonium ion include tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tri-n- octylethylphosphonium ion, cetyltriethylphosphonium ion, cetyltri-n-butylphosphonium ion, n-butyltriphenyl- phosphonium ion, n-amyltriphenylphosphonium ion, n-hexyltriphenylphosphonium ion, n-heptyltriphenyl- phosphonium ion, methyltriphenylphosphonium ion, benzyltriphenylphosphonium ion, tetraphenyl- phosphonium ion, etc. Exemplary anions are the same as described for the anions of the quaternary 45 ammonium salts. These onium salts may be used alone or in admixture of two or more, generally in an amount of about 0.001 to 1 mol, preferably about 0.01 to 0.1 mol per mol of the compound of formula (3). In the practice of the invention, reaction may be carried out by concurrently charging a reactor with the two reactants, onium salt and basic aqueous solution, or by previously charging a reactor with one to three 50 components and subsequently adding the remaining components to the reactor. Most often, a reactor is charged with the two reactants and onium salt and heated to the reaction temperature before the basic aqueous solution is added dropwise to the reactor. The reaction conditions include a temperature of -25 °C to 100°C, preferably 30 °C to 95 °C, more preferably 50 °C to 90 °C and a time of 10 minutes to 8 hours, preferably 30 minutes to 2 hours. 55 The fluorinated glycidyl ether in a second form of the present invention is a fluorinated silicon compound or silicon-modified fluorinated glycidyl ether of the following formula (2).

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Xr.R3-nSi - CH2 - CH2 (CH2)» - C - 0 - CH2 CH - CH2 /\ \ / F3C CF3 0

(2)

10 In formula (2), X is a hydrolyzable group, R is a monovalent organic group, n is an integer of 1 to 3, and m is equal to 0 or 1 . The hydrolyzable group represented by X is preferably selected from the group consisting of F, CI, Br, I, OR1 and NR2R3. R1 is an organic group including alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, i-propyl and n-butyl groups, fluoroalkyl groups having 2 to 15 carbon atoms such as is a trifluoroethyl group, acyl groups such as acetyl and propionyl groups, and alkenyl groups having 2 to 5 carbon atoms such as an isopropenyl group. R2 and R3, which may be the same or different, are alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and isopropyl groups. The organic group represented by R is selected from alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and n-propyl groups, aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl 20 groups, and fluoroalkyl groups having 3 to 15 carbon atoms such as a trifluoropropyl group. Preferred among the compounds of formula (2) are those wherein X is a methoxy, ethoxy or isopropenoxy group and R is a lower alkyl group such as a methyl group. Preferred examples are fluorinated organic silicon compounds of the following formulae (2a) and (2b).

25 CF3

(CH30)3SiCH2CH2COCH2CH - CH2 ... (2a) I \ / CF3 O 30 CF3

(CH30)3SiCH2CH2CH2COCH2CH - CH2 ... (2b)

35 CF3 O

The compound of formula (2) can be synthesized by effecting addition reaction between a fluorinated unsaturated glycidyl ether of formula (1) defined above and a hydrosilane of the following formula (3): 40 XnR3-„SiH (4)

wherein X, R and n are as defined above in the presence of a transition metal or a salt or complex thereof as a catalyst. 45 The amounts of the fluorinated unsaturated glycidyl ether of formula (1) and the hydrosilane of formula (4) are not particularly limited although they are preferably used in a molar ratio of from about 1 :0.8 to about 1:2, more preferably from about 1:1 to about 1:1.5. For promoting reaction between the compounds of formula (1) and (4), a transition metal such as Pt, Rh and Pd, a transition metal salt or a transition metal complex is used as a catalyst alone or in admixture of 50 two or more. Examples of the catalyst include H2PtClG, complexes of H2PtClG with olefins, complexes of H2PtCIG with alcohols, complexes of H2PtCIG with vinylsiloxanes, RhCI3, Rh(CH2COCHCOCH2)3, Rh(PPh3)- 3CI, Rh(PPh3)3Br, Rh2(AcO)+, Rh(PPh3)2(CO)CI, Rh(CH2COCHCOCH2)(CO)2, Rh+(CO)i2, RhG(CO)iG, Rh- (PPh3)3(CO)H, (Nhk)2PdCIG, (NH+fePdCU, Pd(CH2COCHCOCH2)2, Pd(PhCN)2CI2, Pd(PPh3)2CI2, Pd(PPh3)- 4, etc. wherein Ph is phenyl, and Ac is acetyl. 55 As compared with conventional olefins, the reactant of formula (1), especially that of formula (1a) is less susceptible to addition reaction of Si-H to its double bond due to the steric and electronic effects of the two CF3 groups. This problem is effectively overcome by the use of the catalyst, especially rhodium complexes such as Rh(CH2COCHCOCH2)3, Rh(PPh3)3CI, Rh(PPh3)3Br, Rh(PPh3)2(CO)CI, and Rh2(AcO)+. Even when

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H2PtClG and modified catalysts thereof are least effective to produce the end adduct, the rhodium catalysts permit formation of the end adduct under practically acceptable temperature and time conditions. Generally, the amount of the catalyst used is about 1 x 10-2 to 1 x 10_G mol, preferably about 1 x 10-3 to 1 x 10-5 mol per mol of the hydrosilane. 5 This reaction may or may not use a solvent and generally proceeds smoothly in a solvent-free system. The reaction may be carried out by charging a reactor with the hydrosilane and catalyst and subsequently adding dropwise the fluorinated unsaturated glycidyl ether to the reactor. Alternatively, a reactor may be first charged with the fluorinated unsaturated glycidyl ether and catalyst before the hydrosilane is added dropwise. It is also possible to charge a reactor with the two reactants and catalyst io and subsequently heat the reactor to a sufficient temperature for reaction to proceed. In any case, temperature control is necessary since the reaction is exothermic. The reaction temperature is generally about 30 to 200 °C, preferably about 60 to 150°C and the reaction time generally ranges from about 30 minutes to 48 hours. The reaction can be tracked by gas chromatography which ensures monitoring of reactant consumption and end product formation. If reactant consumption stops midway the reaction is process, the reaction can be effectively restarted by feeding an additional catalyst. The reaction product may be purified and isolated by distillation.

EXAMPLE

20 Examples of the present invention are given below by way of illustration and not by way of limitation. All percents are by weight unless otherwise stated.

Example 1

25 A 500-ml three-necked flask equipped with a condenser, dropping funnel, thermometer, and magnetic stirrer was charged with 108.5 grams (0.55 mol) of 1 ,1 ,1-trifluoro-2-trifluoromethyl-3-buten-2-ol, 254.4 grams (2.75 mol) of chloromethyloxirane, and 18.7 grams (0.055 mol) of tetrabutylammonium hydrogen sulfate. With stirring, the mixture was heated to 70 °C. To the flask 146.7 grams (0.55 mol) of an aqueous solution of 15% by weight sodium hydroxide was added dropwise over about 1.5 hours and the mixture was stirred 30 for a further 30 minutes. The reaction solution was allowed to cool to room temperature and separated into an organic layer and an aqueous layer. The organic layer was twice washed with water and dried over 30.0 grams of anhydrous sodium sulfate. After the excess chloromethyloxirane was distilled off, vacuum distillation yielded 89.4 grams of the end product, that is, fluorinated allylglycidyl ether of formula (1a). This product had a boiling point of 81 -82 ° C/8664.5 Pa (65 Torr) and a yield of 65.0%. 35

CH2=CH - C - O - CH2 - CH - CH2 ... (la)

F3C CF3 0 40

This fluorinated allylglycidyl ether was analyzed by proton-NMR spectroscopy, IR spectroscopy, mass spectroscopy and elemental analysis, with the following results. The IR spectrum is shown in FIG. 1.

45 Analytical results

1H-NMR (CCk solution, TMS internal standard, ppm): 2.5-2.8

50 O / \/ (m, 2H H2C - C

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2.9-3.1

(m, 1H c - c -

3.6- 3.8 (m, 2H, -Q-CH2-) 5.7- 5.9 (m, 3H, H2C = CH-) 10 IR (KBr plate method, neat, cm-1): 3010, 2940, 1920, 1645, 1465, 1435, 1410, 1300-1150, 1030, 960, 915, 860, 735 MS (m/e): 251 (m + 1), 233, 221, 73 15 Elemental analysis: C H F Calcd. (%) 38.4 3.2 45.6 20 Found (%) 38.6 3.1 45.4

Example 2 25 A mixture of 1.0 gram (5.2 mmol) of 1 ,1 ,1-trifluoro-2-trifluoromethyl-3-buten-2-ol, 2.4 grams (25.9 mmol) of chloromethyloxirane, 1.4 grams (5.3 mmol) of an aqueous solution of 15% by weight sodium hydroxide, and 0.5 mmol of the phase transfer catalyst shown in Table 1 was heated at 80 °C for 2 hours and then analyzed for composition by gas chromatography. The results are shown in Table 1 . 30

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Table 1

Synthesis of fluorinated allylglycidyl ethers

5 using phase transfer catalysts

Conversion of Yield* of CH2=CH~C-0H CH2=CH - C - 0 - CH2CH - CH2 10 F3C CF3 F3C CF3 X0X (%) (%)

(n-C4H,)4NCl 88 66 75 (n-C;H9)4NBr 84 69

C6H5CH2(CH3)3NC1 92' 73 2Q

(n - C12H25)lQ>Cl 66 45

25 (n-C,H,)4PBr 58 53

* calculated based on the consumed amount of CH2=CH — C — OH 30 /\ F3C CF3

35 Example 3

A 300-ml four-necked flask equipped with a condenser, dropping funnel, thermometer, and magnetic stirrer was charged with 43.3 grams (0.208 mol) of 1 ,1 ,1-trifluoro-2-trifluoromethyl-4-penten-2-ol, 96.2 grams (1.04 mol) of epichlorohydrin, and 7.1 grams (0.021 mol) of tetrabutylammonium hydrogen sulfate. With 40 stirring, the mixture was heated to 85 °C. To the flask 55.5 grams (0.208 mol) of an aqueous solution of 15% weight sodium hydroxide was added dropwise over about 30 minutes and the mixture was stirred for a further 30 minutes at 85 °C. The reaction mixture was allowed to separate into an organic layer and an aqueous layer. The organic layer (lower layer) was twice washed with water, dried over anhydrous sodium sulfate and collected by filtration. Vacuum distillation of this layer yielded 38.7 grams of the end product at 45 a boiling point of 88-90 ° C/6265.1 Pa (47 mmHg). Based on the following analytical results, this product was found to be the fluorinated unsaturated glycidyl ether of formula (1b). The yield was 70%.

CH2=CH - CH2 - C - O - CH2 - CH - CH2 • • • ( lb ) /\ \ / F3C CF3 0

55 Analytical results

19F-NMR (CCU solution, CF3COOH standard): 4.3 ppm (s) 1H-NMR (CCU solution, TMS internal standard):

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2.41-2.66 ppm

0 / \ (m, 2H, -CH-CH2)

2.71 ppm 10 CF3

- ( d , 2 H , - CH_2 - C ) 15 CF3

2.89-3.11 ppm

20 0 / \ (m, 1H, -CH-CH2)

25 3.51-4.00 ppm

(m, 2H, -0-CH2-CH<) 30

4.95-6.11 ppm

35 ( n, 3H, CH2=CH - )

IR: FIG. 2

40 Elemental analysis: C H F Calcd. (%) 40.92 3.82 43.15 Found (%) 40.98 3.75 43.71 45

Example 4

50 A mixture of 1.0 grams (4.8 mmol) of 1 ,1 ,1 ,-trifluoro-2-trifluoromethyl-4-penten-2-ol, 2.2 grams (23.8 mmol) of chloromethyloxirane, 1.3 grams (4.9 mmol) of an aqueous solution of 15% by weight sodium hydroxide, and 0.5 mmol of the phase transfer catalyst shown in Table 2 was heated at 80 ° C for 2 hours and then analyzed for composition by gas chromatography. The results are shown in Table 2.

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Table 2

Synthesis of CH2=CHCH2COCH2CH — CH2

F3C CF3 O using phase transfer catalysts

Conversion of Yield* of CH2=CH-CW;C - OH CH2 5= CH-OfrC - 0 - CH2CH - CH2 Catalyst ^\ /\ \ / F3C CF3 F3C CF3 x(f (%) (%)

(n-C4H,)4NCl 85 70

(n-C4H9)4NBr 8Q 75

C6H5CH2(CH3)3NC1 89 63

- (n C4H25)N^>C1 72 51

(n-C4H9)4PBr 65 60

* calculated based on the consumed amount of CH2=CH-q,-C - OH /\ F3C CF3

bxample 5

A 100-ml stainless steel cylinder was charged with 25.0 grams (0.10 mol) of the compound of formula [la), 14.7 grams (0.12 mol) of (CH30)3SiH, and 0.024 grams (6.0 x 10~5 mol) of Rh(CH2COCHCOCH2)3 and heated at 135° C for 10 hours. To the reaction mixture were additionally admitted 7.3 grams (0.06 mol) Df ((CH30)3SiH and 0.024 grams (6.0 x 10-5 mol) of Rh(CH2COCHCOCH2)3. The mixture was heated at 135 1 C for a further 10 hours. Distillation of the reaction mixture yielded 22.0 grams of the end product, which was found to be the compound of formula (2a) based on the following analytical results. The yield was 59%.

CF3

(CH30)3SiCH2CH2COCH2CH - CH2 ••• (2a)

CF3 O

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Analytical results

19F-NMR (CFgCOOH standard): 4.9 ppm (s) 1H-NMR (TMS internal standard): 0.64-0.93 ppm

(m, 2H, = Si - CH_2 - ) / u

1.93-2.17 ppm

CF3 I (m, 2H, - C - CH2 - )

CF3

2.53-2.86 ppm

(m, 2H, - CH - CH2)

3.06-3.17 ppm ou (m, 1H, — C H — CH2 )

J.bb ppm

(s, 9H, (CH30)3Si - )

3.61-3.79 ppm

(m, 2H7 -O-CH2-CH-)

IR (cm-1): 50 3060 (w), 2955 (s), 2850 (s), 1458 (m), 1280 (s), 1210 (a), 1085 (s), 827 (s)

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Elemental analysis: C H F Si Calcd. (%) 35.48 4.87 30.61 7.54 Found (%) 35.02 4.81 31.15 7.99

Example 6

A 25-ml stainless steel cylinder was charged with 1.0 gram (4.0 mmol) of the compound of formula (1a), 0.59 grams (4.8 mmol) of (CH30)3SiH, and 4.8 x 10-3 mmol of the catalyst shown in Table 3 and heated at 135°C for 10 hours. The contents were analyzed for composition by gas chromatography. The results are shown in Table 3.

Table 3

Catalyzed Synthesis of (CH30)3SiCH2CH2COCH2CH - CH2 / \ \ / F3C CF3 O

25 Conversion of Yield* of CH2=CHCOCH2CH - CH2 ( CH30 ) 3SiCH2CH2COCH2CH - CH2 Catalyst /\ \/ /\ \/ F3C CF3 O FjC CF> u (%) (%) 30 1 2-ethylhexanol- , fin Q modified H2PtCl6

Rh(PPh3)3Cl 7 5 2 2 35

Rh(PPh3)3Br 78 29

40 Rh(OAc), 100 14

Rh(PPh3)2(CO)Cl 64 23

45 Rh(PPh3 )3(CO)H 3'1 21

* calculated based on the comsumed amount of 50 CH2=CHCOCH2CH - CH2 /\ \ / F3C CF3 O

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Example 7

A 200-ml three-necked flask equipped with a condenser, dropping funnel, thermometer, and magnetic stirrer was charged with 26.4 grams (0.10 mol) of the compound of formula (1b) and 0.011 grams (2.8 x 5 10~5 mol) of Rh(CH2COCHCOCH2)3 and heated to 85 °C. To the flask 17.1 grams (0.14 mol) of (CH30)3SiH was added dropwise over 2 hours. The mixture was heated at 80 °C for a further 15 hours. Distillation of the reaction mixture yielded 25.5 grams of the end product, which was found to be the compound of formula (2b) based on the following analytical results. The yield was 66%.

CF3

(CH30)3SiCH2CH2CH2COCH2CH - CH2 ... (2b)

75 CF3 O

Analytical results 20 19F-NMR (CF3COOH standard): 4.7 ppm (s) 1H-NMR (TMS standard): 0.54-0.78 ppm

25 (m, 2H = Si - CH2 - )

1.47-2.11 ppm 30

CF3

( m , 4 H , - C _H2 - C H_2 - C - ) 35 CF

40 2.51-2.84 ppm

(m, 2H, -CH-CH,) O 45

3.04-3.15 ppm so (m, 1H, -CH-CH2) O

3.55 ppm 55

(s, 9H, (CH30)3Si - )

15 EP 0 527 020 B1

3.75-3.81 ppm

(m, 2H, -O-CH2-CHO 5

IR (cm-1): 3060 (w), 2955 (s), 2850 (s), 1464 (m), 1274 (s), 1210 (a), 1090 (s), 818 (s) 10 Elemental analysis: C H F Si Calcd. (%) 37.30 5.22 29.50 7.27 Found (%) 36.98 5.10 28.85 7.51

Example 8 20 A 25-ml stainless steel cylinder was charged with 1 .0 grams (3.8 mmol) of the compound of formula (1b), 0.59 grams (4.8 mmol) of (CH30)3SiH, and 0.047 grams (4.8 x 10-3 mmol) of 2-ethylhexanol-modified H2PtClG and heated at 100°C for 15 hours. The contents were analyzed for composition by gas chromatography. The starting reactant, compound of formula (1b) had been completely consumed. There 25 was obtained the compound of formula (2b) in a yield of 62%.

Example 9

By reacting 26.4 grams (0.10 mol) of the compound of formula (1b) with 14.6 grams (0.14 mol) of a 30 compound of the following formula (4a) in accordance with the procedure of Example 7, 21.4 grams of a compound of the following formula (2c) was obtained in a yield of 58%.

CH3 35 j (4a) C2H5OSiH I CH3 40 CH3 CF3

C2H5OSiCH2CH2CH2COCH2CH - CH2 (2c) I | \ / CH3 CF3 O 45

Example 10

50 By reacting 26.4 grams (0.10 mol) of the compound of formula (1b) with 23.0 grams (0.14 mol) of (C2H50)3SiH in accordance with the procedure of Example 7, 29.1 grams of a compound of the following formula (2d) was obtained in a yield of 68%.

16 EP 0 527 020 B1

CF3

(C2H50)3SiCH2CH2CH2COCH2CH - CH2 (2d) I \ / CF3 0

Claims 10 1. A fluorinated glycidyl ether of the following formula (1)

— (CH2) 15 CH2=CH (1)

20 wherein m is equal to 0 or 1 .

2. A fluorinated glycidyl ether of the following formula (2):

25 [nR3 nS i— CH2— CH2— ( CH2 ) O— CH2— CH— j . ^C— F,C CF, 0 ... (2)

30 wherein X is a hydrolyzable group selected from F, CI , Br, I, OR1 and NR2R3 wherein; R1 is selected from an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 2 to 15 carbon atoms, an acyl group, and an alkenyl group having 2 to 5 carbon atoms; and R2 and R3, which may be the same or different, are alkyl groups having 1 to 10 carbon atoms, R is a monovalent organic 35 group selected from an alkyl group having 1 to 10 atoms, an aryl group having 6 to 10 carbon atoms and a fluoroalkyl group having 3 to 15 carbon atoms, n is an integer of 1 to 3, and m is equal to 0 or 1.

3. A fluorinated glycidyl ether according to claim 2 wherein R is selected from methyl, ethyl, n-propyl, phenyl, tolyl and trifluoropropyl. 40 4. A fluorinated glycidyl ether according to either one of claims 2 or 3 wherein R1 is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, trifluoroethyl, acetyl, propionyl and isopropenyl.

5. A fluorinated glycidyl ether according to any one of claims 2, 3 and 4 wherein R2 and R3 are selected 45 from methyl, ethyl and isopropyl.

6. A fluorinated glycidyl ether according to any one of claims 2, 3, 4 or 5 wherein X is selected from methoxy, ethoxy and isopropenoxy and R is a methyl group.

50 7. A method for preparing a fluorinated glycidyl ether as set forth in claim 1 , comprising the step of: reacting a compound of the following formula (3):

CH2=CH— ( CH2 ) m— C— OH 55 F3C CF3 ... (3)

17 EP 0 527 020 B1

wherein m is equal to 0 or 1 with chloro-methyloxirane in the presence of at least one onium salt selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts in a two phase system of a basic aqueous phase and an organic phase.

5 8. A method for preparing a fluorinated glycidyl ether as set forth in claim 2 comprising the step of: effecting addition reaction between a fluorinated glycidyl ether of the following formula (1):

10 (1)

and a hydrosilane of the following formula (4): 15 XnR3-„SiH (4)

, wherein m, n, R and X have the same meaning as in claim 2, in the presence of a transition metal or a salt or complex thereof as a catalyst. 20 9. A homopolymer, copolymer or silane compound prepared from a fluorinated glycidyl ether according to claim 1.

10. A method according to claim 7 wherein the compound of formula (3) is one of 1,1,1 -trifluoro-2- 25 trifluoromethyl-3-buten-2-ol or 1 ,1 ,1-trifluoro-2-trifluoromethyl-4-penten-2-ol.

11. A method according to claim 7 or claim 10 wherein the ratio of the compound of formula (3) and chloromethyloxirane is in the range 1:1 to 1:50.

30 12. A method according to any of claims 7, 10 or 11 wherein the onium salt is present in an amount of about 0.001 to 1 mol.

Patentanspruche

35 1. Fluorierter Glycidylether der folgenden Formel (1):

CH — CH2 CH2=CH — ( CH, ) a C O CH2 ^ f3c b?3 o •••

worin m gleich 0 oder 1 ist.

45 2. Fluorierter Glycidylether der folgenden Formel (2):

) C— C XnR3 . n S i— CH2— CH2— ( CH2 m— CF,� FX 6 (2) 50 ' ...

worin X eine hydrolysierbare Gruppe, ausgewahlt aus F, CI, Br, I, OR1 und NR2R3, ist, worin: R1 ausgewahlt ist aus einer Alkylgruppe mit 1 - 10 Kohlenstoffatomen, einer Fluoralkylgruppe mit 2 - 15 Kohlenstoffatomen, einer Acylgruppe und einer Alkenylgruppe mit 2 - 5 Kohlenstoffatomen; R2 und 55 R3, die gleich oder verschieden sein konnen, Alkylgruppen mit 1 - 10 Kohlenstoffatomen sind; R eine einwertige organische Gruppe, ausgewahlt aus einer Alkylgruppe mit 1 - 10 Kohlenstoffatomen, einer Arylgruppe mit 6 - 10 Kohlenstoffatomen und einer Fluoralkylgruppe mit 3 - 15 Kohlenstoffatomen, ist; n eine ganze Zahl von 1 - 3 ist; und m gleich 0 oder 1 ist.

18 EP 0 527 020 B1

3. Fluorierter Glycidylether nach Anspruch 2, worin R aus Methyl, Ethyl, n-Propyl, Phenyl, Tolyl und Trifluorpropyl ausgewahlt ist.

4. Fluorierter Glycidylether nach Anspruch 2 oder 3, worin R1 aus Methyl, Ethyl, n-Propyl, i-Propyl, n- 5 Butyl, Trifluorethyl, Acetyl, Propionyl und Isopropenyl ausgewahlt ist.

5. Fluorierter Glycidylether nach irgendeinem der Anspruche 2, 3 und 4, worin R2 und R3 aus Methyl, Ethyl und Isopropyl ausgewahlt sind.

70 6. Fluorierter Glycidylether nach irgendeinem der Anspruche 2, 3, 4 und 5, worin X aus Methoxy, Ethoxy und Isopropenoxy ausgewahlt und R eine Methylgruppe ist.

7. Verfahren zur Herstellung eines fluorierten Glycidylethers nach Anspruch 1 , umfassend den Schritt: Umsetzen einer Verbindung der folgenden Formel (3): 75

20 worin m gleich 0 oder 1 ist, mit Chlormethyloxiran in Gegenwart zumindest eines Onium-Salzes, ausgewahlt aus der Gruppe, bestehend aus quaternaren Ammoniumsalzen und quaternaren Phospho- niumsalzen, in einem Zweiphasen-System aus einer basischen waBrigen Phase und einer organischen Phase. 25 8. Verfahren zur Herstellung eines fluorierten Glycidylethers nach Anspruch 2, umfassend den Schritt: Bewirken einer Additionsreaktion zwischen einem fluorierten Glycidylether der folgenden Formel

35 und einem Hydrosilan der folgenden Formel (4):

XnR3-„SiH (4)

40 worin m, n, R und X dieselbe Bedeutung besitzen wie in Anspruch 2, in Gegenwart eines Ubergangs- metalls oder eines Salzes oder Komplexes davon als Katalysator.

9. Homopolymer-, Copolymer- oder Silan-Verbindung, hergestellt aus einem fluorierten Glycidylether nach Anspruch 1. 45 Verfahren nach Anspruch 7, worin die Verbindung der Formel (3) eine von 1 ,1 ,1 -Trifluor-2-trifluormethyl- 3-buten-2-ol oder 1 ,1 ,1-Trifluor-2-trifluormethyl-4-penten-2-ol ist.

Verfahren nach Anspruch 7 oder 10, worin das Verhaltnis der Verbindung der Formel (3) zu Chlorme- thyloxiran im Bereich von 1 : 1 bis 1 : 50 liegt.

Verfahren nach irgendeinem der Anspruche 7, 10 oder 11, worin das Onium-Salz in einer Menge von etwa 0,001 - 1 Mol vorliegt.

19 EP 0 527 020 B1

Revendicatlons

1. Glycidyl-ether fluore, de la formule (1) suivante :

CH2=CH (CHj),,-

(1)

dans laquelle m est egal a 0 ou 1.

2. Glycidyl-ether fluore, de la formule (2) suivante :

XnR3.nSi— CH2— CH— (CH2) »• 2 V (2)

dans laquelle X est un groupe hydrolysable choisi parmi F, CI, Br, I, OR1 et NR2R3, ou: R1 est choisi parmi un groupe alkyle ayant 1 a 10 atomes de carbone, un groupe fluoroalkyle ayant 2 a 15 atomes de carbone, un groupe acyle et un groupe alcenyle ayant 2 a 5 atomes de carbone ; et R2 et R3, qui peuvent etre identiques ou differents, sont des groupes alkyle ayant 1 a 10 atomes de carbone, R est un groupe organique monovalent choisi parmi un groupe alkyle ayant 1 a 10 atomes, un groupe aryle ayant 6 a 10 atomes et un groupe fluoroalkyle ayant 3 a 15 atomes de carbone, n est un nombre entier de 1 a 3 et m est egal a 0 ou 1 .

3. Glycidyl-ether fluore selon la revendication 2, dans lequel R est choisi parmi methyle, ethyle, n-propyle, phenyle, tolyle et trifluoropropyle.

4. Glycidyl-ether fluore selon I'une quelconque des revendications 2 ou 3, dans lequel R1 est choisi parmi methyle, ethyle, n-propyle, i-propyle, n-butyle, trifluoroethyle, acetyle, propionyle et isopropenyle.

5. Glycidyl-ether fluore selon I'une quelconque des revendications 2, 3 et 4, dans lequel R2 et R3 sont choisis parmi methyle, ethyle et isopropyle.

6. Glycidyl-ether fluore selon I'une quelconque des revendications 2, 3, 4 ou 5, dans lequel X est choisi parmi methoxy, ethoxy, isopropenoxy, et R est un groupe methyle.

7. Methode de preparation d'un glycidyl-ether fluore selon la revendication 1, comprenant les etapes consistant a : faire reagir un compose de formule (3) suivante :

(3)

dans laquelle m est egal a 0 ou 1, avec du chloromethyloxirane en presence d'au moins un sel d'onium choisi dans le groupe constitue par les sels d'ammonium quaternaire et les sels de phosphonium quaternaire, dans un systeme a deux phases constitue d'une phase aqueuse basique et d'une phase organique.

20 EP 0 527 020 B1

8. Methode de preparation d'un glycidyl-ether fluore selon la revendication 2, comprenant les etapes consistant a : effectuer une reaction d'addition entre un glycidyl-ether fluore de la formule (1) suivante :

5 CH2=CH { CH2 ) m— C—

F36 CF3 Q ... (1) 10

et un hydrosilane de la formule (4) suivante :

XnR3-„SiH (4) 15 dans laquelle m, n, R et X ont la meme signification qu'a la revendication 2, en presence d'un metal de transition ou d'un sel ou complexe de celui-ci, en tant que catalyseur.

9. Homopolymere, copolymere ou compose de silane prepare a partir d'un glycidyl-ether fluore selon la 20 revendication 1.

10. Methode selon la revendication 7, dans laquelle le compose de formule (3) est I'un des composes 1 ,1 ,1-trifluoro-2-trifluoromethyl-3-buten-2-ol ou 1 ,1 ,1-trifluoro-2-trifluoromethyl-4-penten-2-ol.

25 11. Methode selon la revendication 7 ou 10, dans laquelle le rapport du compose de formule (3) au chloromethyloxirane est comprise entre 1 : 1 et 1 : 50.

12. Methode selon I'une quelconque des revendications 7, 10 ou 11, dans laquelle le sel d'onium est present en une quantite d'environ 0,001 a 1 mole. 30