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Novel Fluorinated Glycidyl Ethers and Method of Making Them

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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 © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 12.04.95 © Int. CI.6: C07D 303/22, C07F 7/1 8, C08G 65/22 © Application number: 92307024.7 @ Date of filing: 31.07.92 © Novel fluorinated glycidyl ethers and method of making them. ® 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. 3 EP 0 527 020 B1 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.
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