CA1302638C - Fluorine-containing cyclic polymer - Google Patents
Fluorine-containing cyclic polymerInfo
- Publication number
- CA1302638C CA1302638C CA000574687A CA574687A CA1302638C CA 1302638 C CA1302638 C CA 1302638C CA 000574687 A CA000574687 A CA 000574687A CA 574687 A CA574687 A CA 574687A CA 1302638 C CA1302638 C CA 1302638C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- polymerization
- fluorine
- repeating units
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920005565 cyclic polymer Polymers 0.000 title description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 115
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 32
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 10
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 claims abstract description 9
- 239000000460 chlorine Chemical group 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLKWQAQYRNTVKF-UHFFFAOYSA-N 1,1,2,3,3,4,5-heptafluoro-5-(1,2,3,3,4,5,5-heptafluoropenta-1,4-dienoxy)penta-1,4-diene Chemical compound FC(F)=C(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)=C(F)F XLKWQAQYRNTVKF-UHFFFAOYSA-N 0.000 claims description 3
- JWKJOADJHWZCLL-UHFFFAOYSA-N 1,2,3,4,5,5,6,6,6-nonafluoro-1-(1,2,3,4,5,5,6,6,6-nonafluorohexa-1,3-dienoxy)hexa-1,3-diene Chemical compound FC(OC(F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F JWKJOADJHWZCLL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 53
- 239000011521 glass Substances 0.000 description 20
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 16
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 16
- 239000003708 ampul Substances 0.000 description 15
- 238000007872 degassing Methods 0.000 description 12
- 238000007710 freezing Methods 0.000 description 12
- 230000008014 freezing Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 description 1
- MHNPWFZIRJMRKC-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound F[C]=C(F)F MHNPWFZIRJMRKC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241001050985 Disco Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 101100273965 Solanum lycopersicum HCR9-0 gene Proteins 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
Abstract
ABSTRACT
A fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2); the polymer having a molecular weight such that the intrinsic viscosity thereof may become at least 0.1.
A fluorine-containing thermoplastic resinous polymer which consists essentially of:
i) a group (a) of repeating units to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2), and ii) a group (b) of repeating units to be represented by the following general formula:
?CF2-CFX?
(where: X is selected from fluorine, chlorine.
O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) the polymer containing therein at least 80% by weight of the group of repeating units (a), and having a molecular weight such that the intrinsic viscosity thereof may be become at least 0.1.
A fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2); the polymer having a molecular weight such that the intrinsic viscosity thereof may become at least 0.1.
A fluorine-containing thermoplastic resinous polymer which consists essentially of:
i) a group (a) of repeating units to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2), and ii) a group (b) of repeating units to be represented by the following general formula:
?CF2-CFX?
(where: X is selected from fluorine, chlorine.
O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) the polymer containing therein at least 80% by weight of the group of repeating units (a), and having a molecular weight such that the intrinsic viscosity thereof may be become at least 0.1.
Description
1~02638 Our Ref.: ~A-493 (F88-30) NOVEL FLUORINE-CONTAINING CYCLIC POLYMER
This invention relates to a novel fluorine-containing cyclic polymer, and, more particularly, it is concerned with a thermoplastic resinous fluorine-containing cyclic polymer having a particular asymmetrical cyclic structure in the main chain thereof.
With regard to the cyclic polymerization of hydrocarbon-type monomers, there have been done various researches, and a multitude of reports have been known in general, inclusive of three-membered cyclic polyether to large-membered cyclic polyether.
On the other hand, there have been known various fluorine-containing polymers, of which polytetrafluoroethylene and many others are already practically put into industrial use.
However, most of these fluorine-containing polymers contain therein the main chain in straight form based on vinyl monomer such as fluoro-olefin, (meth)acrylate having the fluoro-alkyl group in its side chain, etc.
There is very few example of polymer to be obtained 13026~8 by cyclic polymerization of a fluorine-type monomer, and it has only been known that a compound of a general formula: CF2=CF(CF2)xCF-CF2 (where: x is an integer of from 1 to 3) undergoes the cyclic polymerization by the y-rays (vide: L.A. Waal, Fluoropolymer, Wiley-Science, 4, High Pressure Polymerization, p 127). It has also been known that a compound represented by the following general formula: CF2=CF-CF2-CFCl-CF2CF=CF2 is polymerized to yield a trasparent and highly elastic film which is excellent in its heat-resistance and oxidation-resistance (vide: D. S. Ballantine et at., U.S. Atomic Energy Comission, BNL-296 (T-50) 18, 1954). However, all these polymers do not contain the ether bond in its principal chain, on account of which they can not be said to be necessarily satisfactory in their transparency and flexibility.
Moreover, British patent specification ~o. 1,106,344, United States patent specification No. 3,418,302, and others described fluorine-containing cyclic polymers which contain in the main chain thereof a cyclic structure having the ether bond to be represented by the following general formula:
~CF2 ~CF2-CF-CF-CF2~
-~CF2-CF fF ~ and/or O
CF2_cF
the polymers being produced by polymerization in a thin solution of perfluorodimethylene-bis(perfluorovinyl ether) as the starting material. This cyclic structure in the main chain of the polymer is, however, symmetrical, hence difficulty is accompanied in its synthesis. There is also apprehension such that the polymer is defectively inferior in its solubility and transparency.
It is therefore an object of the present invention to provide a novel fluorine-containing thermoplastic resinous polymer having in the main chain thereof an asymmetrical cyclic structure having the ether bond, which has not been known heretofore.
With a view to solving the above-described problems inherent in the conventional fluorine-containing cyclic polymers, the present invention provides the novel fluorine-containing thermoplastic resinous polymers, as follows:
*a fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula:
-~CF2-CF / CFt- and/or -tCF2-CF-fF-CF2~-OtCF2)n O--~CF2)n 130~638 (where: n is an integer of 1 or 2), said polymer having a molecul~r weight such that the intrinsic viscosity of the polymer become at least 0.1;
*a fluorine-containing thermoplastic resinous polymer which consists essentially of:
i) a group (a) of repeating units to be represented by the following general formula:
/CF2\
~C 2 C\ /CFt- and/or -~CF2-fF-CIF-CF2 t OtC 2)n O--~CF2)n ~where: n is an integer of 1 or 2); and ii) a group ~b) of repeating unit to be represented by the following general formula:
~CF2-CFX 3 ~where: X is selected from fluorine, chlorine, O-C~2CF2CF3, O-CF2CF~CF3)OCF2CF2SO2F~ and O-CF2CF2CF2COOCH3), said polymer containing therein at least 80% by weight of the group (a) of repeating units, and having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
The group ~a) of the repeating units according to the present invention can be obtained by fluorination of a `'130;~638 partially fluorinated vinyl ether, for example, CF2=CF-O-CF2CF2-CH=CH2, after it has been subjected to the cyclic polymerization. Preferably, however, the group (a) of the repeating units can be obtained by subjecting perfluoroallyl vinyl ether (hereinafter abbreviated as "PAVE" ) or perfluorobutenyl vinyl ether (hereinafter abbreviated as "PBVE" ), which is represented by the following general formula:
CF2=CF-0 ( CF2 ) nCF=CF2 (where: n is an integer of 1 or 2) to the radical cyclic polymerization. In more detail, when PAVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=1, and, when PBVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=2.
This dicovery is very surprising, because perfluorodiolefin which has so far been known yields a cross-linked polymer in general, while perfluorodimethylene-bis(perfluorovinyl ether), etc.
yields a soluble polymer containing the cyclic structure in its main chain, only when it is polymerized in a thin solution.
PAVE is described in Japanese Patent Publication No.
45619/1985. PBVE can be synthesized by de-chlorination 130~638 of CF2=CF-O-CF2-CF2-CClF-CClF2 with use of zinc.
More surprising is that PAVE and PBVE are copolymerizable at an arbitrary ratio, hence there can be obtained a copolymer having the repeating units of n=l, n=2 at an arbitrary ratio.
The polymer which contains therein the group (a) of these repeating units is a transparent resin and is soluble in a fluorine type solvent such as perfluoro(2-butyltetrahydrofuran). Also, from the measurement of the infrared ray absorption spectrum, there can be recognized no absorption in the vicinity of 1790 cm 1 due to the double bond.
Incidentally, the preferred cyclic structure to be obtained are those five-membered and six-membered ring structures which has less distortion.
Furthermore, perfluorovinyl ether to be represented by the general formula: CF2=CF-O(CF2)nCF=CF2 (where: n is an integer of 1 or 2) is radically copolymerized with a comonomer to be represented by the following general formula: CF2=CFX (where: X is selected from fluorine, - chlorine, O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) to thereby yield a copolymer which consists essentially of:
i) a group (a) of repeating units of the cyclic structure to be represented by the following general formula:
13~;3~
& ~CF2 -fF-CF-CF
O (CF2)n 0--~C2)n (where: n is an integer of 1 or 2); and ii) a group (b) of repeating units to be represented by the following general formula:
-~CF2-CFX~-~where: X is selected from fluorine, chlorine O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3 ) .
The comonomer to be represented by the following general formula has already been known:
CF2=CFX
(where: X is selected from fluorine, chlorine, O-CF2CF2CF3, O-CF2CF~CF3)OCF2CF2SO2F~ and O-CF2CF2CF2COOCH3).
In order to obtain a transparent and solvent-soluble polymer, it is preferable that 80~ by weight or more of the group (a) of the repeating units be contained in the polymer. In case the content of this group (a) of the repeating units is less than 80~ by weight, the resin i:~O2638 loses its transparency, solvent-solubility and mechanical strength.
Molecular weight of this polymer should preferably be such that its intrinsic viscosity may become 0.1 or above. When the intrinsic viscosity is below 0.1, the mechanical strength of the resin becomes impractically low.
As the method for polymerization of these polymers, there may be employed the radical polymerization. That is to say, the polymerization method is not at all restricted to any specific one, provided that the polymerization proceeds radically. Examples are those polymerizations, in which use is made of an inorganic radical initiator, light rays, ionizing radiation, or heat. The polymerization method is also not particularly limited, and there may be used the bulk-polymerization, solution-polymerization, suspension-polymerization, and emulsion-polymerization.
Molecular weight of the polymer is controllable depending on polymerization temperature, concentration of the initiator, and so on. A chain transfer agent may also be used.
The polymerization composition of the copolymer can be controlled by the charging ratio of each and every comonomer to be used for the polymerization.
Depending on the kind of comonomers to be used and the rate of polymerization, it is possible to regulate g the properties of the copolymer resin to be obtained, such as solubility, glass transition point r rupture strength, elongation, yield stress, modulus of elasticity, adhesivity to base material, and so forth.
Also, depending on the kind of the comonomer, it is possible to control the polymerization speed during the polymerization.
Use of tetrafluoroethylene for the comonomer makes it possible to lower the glass transition temperature of the resulting copolymer and to increase the polymerization speed. Addition of chlorotrifluoroethylene to the comonomer causes solubility of the copolymer to vary.
Use of CF2=CF-O-CF2CF2CF3 as the comonomer improves elongation of the resulting copolymer. When use is made of CF2=cF-o-cF2cF(cF3)-o-cF2cF2so2F or CF2=CF-O-CF2CF2CF2COOCH3 as the comonomer, adhesivity of the resulting copolymer to the base material would increase. It is of course feasible to use two or more kinds of the comonomers.
The polymer consisting of these groups (a) and (b) of the repeating units is transparent, and soluble in those fluorine type solvents such as perfluoro(2-butyltetrahydrofuran), etc. Also, measurement of the infrared ray absorption spectrum reveals no absorption taken place in the vicinity of 1790 cm l due to the double bond. The composition of the copolymer is determined by the l9F-NMR spectrum ~302638 measurement and the elementary analyses. Incidentally, the preceeding e~planations are only for assisting the good understanding of the present invention, hence it goes without saying that they are not intent on limiting the scope of the present invention.
In the following, the present invention will be explained in further details in reference to preferred and actual examples thereof. It should also be understood that these examples are only illustrative of the present invention and do not intend to limit the scope of the present invention.
30 g of PAVE and 0.3 g of diisopropyl-peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 25C. The pressure during the polymerization was lower than the atmospheric pressure. After the polymerization reaction, there was obtained 4.5 g of a polymer.
Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinity of 1790 cm 1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its 19F-NMR spectrum was measured, there was obtained a spectrum which indicated to the following repeating structure.
/ CF~
-tCF2-CF CF~
\O-C~2 The intrinsic viscosity of this polymer [ n ] was 0.50 at 30C in liquid which is composed principally of "FLORINATE FC-75" (a tradename for perfluoro(2-butyltetrahydrofuran) of 3M Corp., U.S.A.
which will hereinafter be abbreviated as "FC-75"). This indicates that the polymer has high degree of polymerization.
The glass transition point of this polymer was 69C, At a room temperature, this polymer indicated a state of its being tough and transparent glass. Further, its 10%
thermal decomposition temperature was 462C, which indicated that the polymer had high thermal stability.
Furthermore, this polymer had colorless transparency, a low refractive index of 1.34, and a high light transmission factor of 95~.
The gas permeability coefficient of this polymer to various gasses was measured, the results of the measurement being shown in the following Table.
13~2638 Gas Permeation Coefflcient (cm3cm/cm2sec. cmHg) He106 x lO lO
H226 x lO lO
C2 8.2 x lO-l 23 9 x lO-l N2 0.81 x lO lO
CH4 0.21 x lO lO
EXAMPLE 2 "
10 g of PAVE, lO g of trichlorotrifluoroethane (hereinafter abbreviated as "R-113~), and lO mg of diisopropylperoxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass.
After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 14 hours at 40C. The pressure during the polymerization was lower than the atmospheric pressure.
As the result, there was obtained 6.1 g of a polymer.
The intrinsic viscosity of this polymer [~ ] was 0.37 at 30C in "FC-75", hence the resulted polymer was found to have a high molecular weight. It was also disco,vered from the l9F-NMR spectrum measurement that the polymer was similar to that obtained in Example 1 above.
~1302638 EXAI'IPLE 3 30 g of PAVE and 10 mg of the polymerization initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 30C. The pressure during the polymerization was lower than the atmospheric pressure.
After the polymerization reaction, there was obtained 16 g of a polymer.
The intrinsic viscosity of this polymer [~ ] was 0.505 at 30 C in "FC-75".
(Synthesis of CF2=CFCF2CF2OCF=CF2) 2,000 g of CF2ClCFClCF2COF was reacted with hexafluoropropyleneoxide in the presence of cesium fluoride, and was further converted into potassium salt thereof by use of potassium hydroxide, after which the substance was subjected to thermal decomposition, thereby obtaining CF2ClCFClCF2CF2OCF=CF2 as the product.
Subsequently, this product was reacted with a mixture of Zn and dioxane to carry out dechlorination, thereby obtaining 300 g of CF2=CFCF2CF2OCF=CF2 (PBVE) having boiling point of 64C. The structure of this fluorine-containing monomer was verified by measurèment of 19F-NMR spectrum.
130:~638 E~AMPLE 4 5.42 g of PBVE as obtained in the above-described Example of Synthesis l and 10 mg of the polymerization o initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After the degassing under freezing condition was repeated for two times, the polymerization reaction was conducted for 48 hours at 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. From this polymerization reaction, there was obtained 2.22 g of a polymer.
When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm 1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its l9F-NMR spectrum was measured, there was obtained a spectrum which indicated the following repeating structure.
~CF2 --tCF2 fF CF~- or ~CF2-CF-CF-CF2) The intrinsic viscosity of this polymer [ n ] was 0.55 at 30C in "FC-75", which indicated that this polymer had ~30:~638 a high degree of polymerization.
The glass transition temperature of this polymer was 108C. At a room temperature, this polymer indicated at state of its being tough and transparent glass. Also, it had 10% thermal decomposition temperature of 457C, thus indicating its high thermal stability. By the way, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as high as 95%, 5 g of PAVE, 5 g of PBVE and lO mg of the o polymerization initiator (C3F7CO)2 were placed in a glass reactor having an inner volume of 60 ml. After the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25C, while agitating the reactants. The pressure during the polymerization reaction as lower than the atmospheric pressure. As the result, there was obtained 5.5 g of a Plymer.
When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm l to be derived from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene and its 19F_NMR spectrum was measured to verify its structure. As the result, the obtained ~302638 polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
~C 2 \ /CF t and a unit of thè cyclic structure to be derived from PBVE
such as represented by the following formula:
~ F2 \ -~CF2-fF-fF-CF2~~;
15C~2 \ /
and containing therein 54% by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer was found to have its intrinsic viscosity [~ ] of 0.44 at 30C in "FC-75", hence high degree of polymerization.
The glass transition point of this polymer was 91C
and indicated a state of its being tough and transparent glass at a room temperature. Further, its 10% thermal decomposition temperature was 435C, thus indicating that the polymer had high thermal stability. Furthermore, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as~high as 95%.
i302638 E~AMPLE 6 5 g of PAVE, 15 g of "R-113", and 80 mg of 5 wt~
solution of the polymerization initiator (C3F7~0)2 were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for three times, O.S g of CF2=CF2 was charged into the reaction system. While shaking the ampoule in an incubator, the polymerization was conducted for six hours at 30C, as the result of which a solid substance was obtained in quantity of 1.5 g .
The thus obtained solid substance was dissolved in perfluorobenzene, and its structure was verified by measurement of 19F-NMR spectrum, from which it was found that the resulted polymer was a copolymer consisting of:
a unit of the cyclic structure to be derived from PAVE
as represented by the following formula:
/CF ~
(CF2-C~ / CF) and a unit of the structure to be derived from CF2=CF2 as represented by the following formula:
(CF2-CF2) and containing therein 81~ by weight of the unit of the cyclic structure to be derived from PAVE. Also, this polymer had its intrinsic~viscosity [~ ] of 0.425 at 30C
~302638 in "FC-75".
20 g of PBVE obtained in Example of Synthesis 1 and 40 mg of the polymerization inltiator (C3F7~0)2 were placed in an ampoule having an inner volume oE 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 1.0 g of CF2=CFCl was charged into the reaction system.
While shaking the ampoule in an incubator, the polymerization reaction was conducted for 10 hours at 25C. As the result, there was obtained a polymer in a quantity of 4.5 g.
Upon measurement of the infrared ray absorption spectrum of this polymer, it was found that there was no absorption in the vicinity of 1790 cm 1 due to the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved into perfluorobenzene, and its structure was verified by measurement of the 19F-NMR spectrum. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula:
C Fz ~ C F 2 - C F-C F - C
C F2 - C F C F ~ or O C F2 o C ~2 i302638 and a unit of the structure to be derived from CF2=CFCl as represented by the following formula.
~ CF2-CFCl~;
and containing therein 84% by weight of the unit of the cyclic structure to be derived from PBVE. This polymer had its intrinsic viscosity of 0.43 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer was in a state of its being tough and transparent glass at a room temperature. It had also a 10% thermal decomposition temperature of 421C, which showed that it had high thermal stability. Further, the polymer showed its solubility in a mixed solution of "FC-75" and "R-113".
20 g of PBVE obtained in Example of Synthesis 1 above and 20 mg of the polymerization initiator (C3F7~0)2 were placed in an ampoule having an inner volume of 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 0.5 g of CF2=CF2 was charged in the reaction system. While shaking this ampoule in an incubator, the polymerization reaction was conducted for five hours at a temperature of 25C. As the result, there was obtained ; 5.8 g of a polymer.
Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinit~ of 1790 cm 1 to be derived ~30;2~38 from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the result of this, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula:
~CF2 (CF2-lCF ÇF~-- or (CF2-CF-CF-CF2~--;
\ /1F2 \ /
. CF2 and a unit of the structure to be derived from CF2=CF2 as represented by the following formula:
~ CF2 -CF2~
and containing therein 94~ by weight of the unit of the cyclic structure to be derived from PBVE. Further, this polymer had its intrinsic viscosity [~ ] of 0.53 in "FC-75" at 30C, thus indicating that it had high degree ` of polymerization. It also indicated a state of its being a tough and transparent polymer at a room temperature.
9 g Of PAVE, 1 g of CF2=CF-O-CF CF CF COOCH and 10 mg of the polymerization initiator (C3F7CO) 2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 24 hours at a temperature of 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained 3.55 g of a polymer.
This polymer was dissolved in perfluorobenzene to measure its 19F-NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
fF~
(CF2-CF ,CF~- and \O-C/F2 a u~t of the structure of the formula:
(CF2-CF~--~ CF2 CF 2 CF 2COOH3, and containing therein 93~ by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer had its intrinsic viscosity [ ~ ] of 0.32 in "FC-75l- at 30C, thus indicating that it had a high degree of polymerization.
The polymer had its glass transition point of 64C, and indicated a state of its being tough and transparent glass. Also, its 10% thermal decomposition temperature i3~2~38 was 430C, thus indicating that it had high thermal stability. Further, this polymer was colorless transparent.
40 g of PAVE~ 5 g of CF2=CF-O-cF2cF2cF2coocH3, and lO
mg of diisopropyl peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass.
After repetition of the degassing under freezing condition for two times, 5 g of CF2=CF2 was charged into the reaction system. While shaking this ampoule in an incubator, the polymerization was conducted for 72 hours at a temperature of 30C. As the result, there was obtained 11.8 g of a polymer.
This polymer was dissolved in perflurobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as 20 represented by the following formula:
\b-C/F2 and units of the formulaS:
(C 2 fF~-- and (CF2CF2~';
OCF2CF2CF2COOcH3 derived from CF2=CF-O-CF2~CF2CF2COOCH3 and CF2=CF2, respectively, and containing therein 82% by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer had its intrinsic viscosity ~ n ] of 0.42 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer was found to have its glass transition point of 58C, and indicated a state of its being tough and transparent polymer at a room temperature. Further, its 10% thermal decGmposition temperature was 421C, thus indicating that it had high thermal stability.
Furthermore, the polymer was colorless transparent.
8 g of PBVE, 1 g of CF2=CFOCF2CF(CF3)OCF2CF2SO2F and 10 mg of the polymerization initiator (C3F7C0)2 were palced in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the consequence, there was obtained 3.8 g of a polymer. This polymer was dissolved in perfluorobenzene to measure its 19F-NMR
spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure i302638 to be derived from PBVE such as represented by the following formula:
/ ~CF~ or (CF2-CF-C\F-CF2~- ;
\ / 2 \C /
and a unit of the structure to be derived from CF2=CFOCF2CF(CF3)OCF2CF2SO2F as represented by the following formula:
~CF2-CF ~
~ ) 'F2CFOCF2CF2SO2F ;
and containing therein 94~ by weight of the unit of the structure to be derived from PBVE.
It was found that this polymer had its intrinsic viscosity [ n ] of 0.38 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer had its glass transition point of 92C, and indicated a state of its being tough and transparent glass. The polymer was colorless transparent. The adhesive property of this polymer with glass was satisfactory.
:;
13026~8 E~AMPLE 12 8 g of PAVE, 2 g of CF2=CF-O-CF2CF2CF3, and lO mg oE
the polymerization initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was coducted for 24 hours at a temperature of 25~C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained a polymer in a quantity of 1.85 g.
This polymer was dissolved in perfluorobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the consequence, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
C~CF2~
20 2 --~CF2- /CF~- ; and a unit of the structure to be derived from CF2=CF-O-CF2CF2CF3 as represented by the following formula:
~CF2-fF2~
, and containin~ therein 89% by weight of the unit of the cyclic structure to be de~ived from PAVE.
1~02638 It was further found that this polymer had its intrinsic viscosity [~ ] of 0.35 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer had its glass transition point of 61C, and indicated a state of its being tough and transparent glass. Furtnermore, its 10~ thermal decomposition temperature was 415C, thus indicating that the polymer had high thermal stability. Moreover, this polymer was colorless transparent, and showed its elongation of 250 at 25C.
The fluorine-containing thermoplastic resinous polymer according to the present invention, containing therein the ether bond in its main chain which has not so far been known, can be readily subjected to press-molding, extrusion-molding, and injection-molding, and, when the polymer is molded into optical parts such as lenses, it exhibits remarkable effect such that the molded article is excellent in its transparency, with added superiority in its chemical-resistant property, electrical insulation, heat-stability, strong acid resistant property, strong alkali resistant property, water-resistant property, moisture-resistant property, and so forth. Further, the polymer according to the present invention possesses high transmiss~bility to the ultraviolet rays, which provides a remarkable effect such that it can substitute various sorts of optical parts i302638 made of quartz glass. Furthermore, since it has high transmissibility to the infrared rays, it can be effectively empolyed for various sorts of infrared ray sensors. Also, the polymer according to the present invention has a low refractive index, in account of which it exhibits an effect such that, when this polymer is prepared into a solution and coated on the surface of the optical parts such as lenses, the light reflection can be reduced. Moreover, the resinous polymer according to the present invention is recognized to be effectively and suitably applicable as the cladding materiai for the optical fibers, material for opto-magnetic discs, p~otective membranes for the solar batteries, gas-separating membranes, protective films for transparent resins such as acrylic resin, polycarbonate resin, and diethylene glycol-bis-(allylcarbonate) resin, etc., and treatment agent for textile materials.
This invention relates to a novel fluorine-containing cyclic polymer, and, more particularly, it is concerned with a thermoplastic resinous fluorine-containing cyclic polymer having a particular asymmetrical cyclic structure in the main chain thereof.
With regard to the cyclic polymerization of hydrocarbon-type monomers, there have been done various researches, and a multitude of reports have been known in general, inclusive of three-membered cyclic polyether to large-membered cyclic polyether.
On the other hand, there have been known various fluorine-containing polymers, of which polytetrafluoroethylene and many others are already practically put into industrial use.
However, most of these fluorine-containing polymers contain therein the main chain in straight form based on vinyl monomer such as fluoro-olefin, (meth)acrylate having the fluoro-alkyl group in its side chain, etc.
There is very few example of polymer to be obtained 13026~8 by cyclic polymerization of a fluorine-type monomer, and it has only been known that a compound of a general formula: CF2=CF(CF2)xCF-CF2 (where: x is an integer of from 1 to 3) undergoes the cyclic polymerization by the y-rays (vide: L.A. Waal, Fluoropolymer, Wiley-Science, 4, High Pressure Polymerization, p 127). It has also been known that a compound represented by the following general formula: CF2=CF-CF2-CFCl-CF2CF=CF2 is polymerized to yield a trasparent and highly elastic film which is excellent in its heat-resistance and oxidation-resistance (vide: D. S. Ballantine et at., U.S. Atomic Energy Comission, BNL-296 (T-50) 18, 1954). However, all these polymers do not contain the ether bond in its principal chain, on account of which they can not be said to be necessarily satisfactory in their transparency and flexibility.
Moreover, British patent specification ~o. 1,106,344, United States patent specification No. 3,418,302, and others described fluorine-containing cyclic polymers which contain in the main chain thereof a cyclic structure having the ether bond to be represented by the following general formula:
~CF2 ~CF2-CF-CF-CF2~
-~CF2-CF fF ~ and/or O
CF2_cF
the polymers being produced by polymerization in a thin solution of perfluorodimethylene-bis(perfluorovinyl ether) as the starting material. This cyclic structure in the main chain of the polymer is, however, symmetrical, hence difficulty is accompanied in its synthesis. There is also apprehension such that the polymer is defectively inferior in its solubility and transparency.
It is therefore an object of the present invention to provide a novel fluorine-containing thermoplastic resinous polymer having in the main chain thereof an asymmetrical cyclic structure having the ether bond, which has not been known heretofore.
With a view to solving the above-described problems inherent in the conventional fluorine-containing cyclic polymers, the present invention provides the novel fluorine-containing thermoplastic resinous polymers, as follows:
*a fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula:
-~CF2-CF / CFt- and/or -tCF2-CF-fF-CF2~-OtCF2)n O--~CF2)n 130~638 (where: n is an integer of 1 or 2), said polymer having a molecul~r weight such that the intrinsic viscosity of the polymer become at least 0.1;
*a fluorine-containing thermoplastic resinous polymer which consists essentially of:
i) a group (a) of repeating units to be represented by the following general formula:
/CF2\
~C 2 C\ /CFt- and/or -~CF2-fF-CIF-CF2 t OtC 2)n O--~CF2)n ~where: n is an integer of 1 or 2); and ii) a group ~b) of repeating unit to be represented by the following general formula:
~CF2-CFX 3 ~where: X is selected from fluorine, chlorine, O-C~2CF2CF3, O-CF2CF~CF3)OCF2CF2SO2F~ and O-CF2CF2CF2COOCH3), said polymer containing therein at least 80% by weight of the group (a) of repeating units, and having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
The group ~a) of the repeating units according to the present invention can be obtained by fluorination of a `'130;~638 partially fluorinated vinyl ether, for example, CF2=CF-O-CF2CF2-CH=CH2, after it has been subjected to the cyclic polymerization. Preferably, however, the group (a) of the repeating units can be obtained by subjecting perfluoroallyl vinyl ether (hereinafter abbreviated as "PAVE" ) or perfluorobutenyl vinyl ether (hereinafter abbreviated as "PBVE" ), which is represented by the following general formula:
CF2=CF-0 ( CF2 ) nCF=CF2 (where: n is an integer of 1 or 2) to the radical cyclic polymerization. In more detail, when PAVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=1, and, when PBVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=2.
This dicovery is very surprising, because perfluorodiolefin which has so far been known yields a cross-linked polymer in general, while perfluorodimethylene-bis(perfluorovinyl ether), etc.
yields a soluble polymer containing the cyclic structure in its main chain, only when it is polymerized in a thin solution.
PAVE is described in Japanese Patent Publication No.
45619/1985. PBVE can be synthesized by de-chlorination 130~638 of CF2=CF-O-CF2-CF2-CClF-CClF2 with use of zinc.
More surprising is that PAVE and PBVE are copolymerizable at an arbitrary ratio, hence there can be obtained a copolymer having the repeating units of n=l, n=2 at an arbitrary ratio.
The polymer which contains therein the group (a) of these repeating units is a transparent resin and is soluble in a fluorine type solvent such as perfluoro(2-butyltetrahydrofuran). Also, from the measurement of the infrared ray absorption spectrum, there can be recognized no absorption in the vicinity of 1790 cm 1 due to the double bond.
Incidentally, the preferred cyclic structure to be obtained are those five-membered and six-membered ring structures which has less distortion.
Furthermore, perfluorovinyl ether to be represented by the general formula: CF2=CF-O(CF2)nCF=CF2 (where: n is an integer of 1 or 2) is radically copolymerized with a comonomer to be represented by the following general formula: CF2=CFX (where: X is selected from fluorine, - chlorine, O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) to thereby yield a copolymer which consists essentially of:
i) a group (a) of repeating units of the cyclic structure to be represented by the following general formula:
13~;3~
& ~CF2 -fF-CF-CF
O (CF2)n 0--~C2)n (where: n is an integer of 1 or 2); and ii) a group (b) of repeating units to be represented by the following general formula:
-~CF2-CFX~-~where: X is selected from fluorine, chlorine O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3 ) .
The comonomer to be represented by the following general formula has already been known:
CF2=CFX
(where: X is selected from fluorine, chlorine, O-CF2CF2CF3, O-CF2CF~CF3)OCF2CF2SO2F~ and O-CF2CF2CF2COOCH3).
In order to obtain a transparent and solvent-soluble polymer, it is preferable that 80~ by weight or more of the group (a) of the repeating units be contained in the polymer. In case the content of this group (a) of the repeating units is less than 80~ by weight, the resin i:~O2638 loses its transparency, solvent-solubility and mechanical strength.
Molecular weight of this polymer should preferably be such that its intrinsic viscosity may become 0.1 or above. When the intrinsic viscosity is below 0.1, the mechanical strength of the resin becomes impractically low.
As the method for polymerization of these polymers, there may be employed the radical polymerization. That is to say, the polymerization method is not at all restricted to any specific one, provided that the polymerization proceeds radically. Examples are those polymerizations, in which use is made of an inorganic radical initiator, light rays, ionizing radiation, or heat. The polymerization method is also not particularly limited, and there may be used the bulk-polymerization, solution-polymerization, suspension-polymerization, and emulsion-polymerization.
Molecular weight of the polymer is controllable depending on polymerization temperature, concentration of the initiator, and so on. A chain transfer agent may also be used.
The polymerization composition of the copolymer can be controlled by the charging ratio of each and every comonomer to be used for the polymerization.
Depending on the kind of comonomers to be used and the rate of polymerization, it is possible to regulate g the properties of the copolymer resin to be obtained, such as solubility, glass transition point r rupture strength, elongation, yield stress, modulus of elasticity, adhesivity to base material, and so forth.
Also, depending on the kind of the comonomer, it is possible to control the polymerization speed during the polymerization.
Use of tetrafluoroethylene for the comonomer makes it possible to lower the glass transition temperature of the resulting copolymer and to increase the polymerization speed. Addition of chlorotrifluoroethylene to the comonomer causes solubility of the copolymer to vary.
Use of CF2=CF-O-CF2CF2CF3 as the comonomer improves elongation of the resulting copolymer. When use is made of CF2=cF-o-cF2cF(cF3)-o-cF2cF2so2F or CF2=CF-O-CF2CF2CF2COOCH3 as the comonomer, adhesivity of the resulting copolymer to the base material would increase. It is of course feasible to use two or more kinds of the comonomers.
The polymer consisting of these groups (a) and (b) of the repeating units is transparent, and soluble in those fluorine type solvents such as perfluoro(2-butyltetrahydrofuran), etc. Also, measurement of the infrared ray absorption spectrum reveals no absorption taken place in the vicinity of 1790 cm l due to the double bond. The composition of the copolymer is determined by the l9F-NMR spectrum ~302638 measurement and the elementary analyses. Incidentally, the preceeding e~planations are only for assisting the good understanding of the present invention, hence it goes without saying that they are not intent on limiting the scope of the present invention.
In the following, the present invention will be explained in further details in reference to preferred and actual examples thereof. It should also be understood that these examples are only illustrative of the present invention and do not intend to limit the scope of the present invention.
30 g of PAVE and 0.3 g of diisopropyl-peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 25C. The pressure during the polymerization was lower than the atmospheric pressure. After the polymerization reaction, there was obtained 4.5 g of a polymer.
Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinity of 1790 cm 1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its 19F-NMR spectrum was measured, there was obtained a spectrum which indicated to the following repeating structure.
/ CF~
-tCF2-CF CF~
\O-C~2 The intrinsic viscosity of this polymer [ n ] was 0.50 at 30C in liquid which is composed principally of "FLORINATE FC-75" (a tradename for perfluoro(2-butyltetrahydrofuran) of 3M Corp., U.S.A.
which will hereinafter be abbreviated as "FC-75"). This indicates that the polymer has high degree of polymerization.
The glass transition point of this polymer was 69C, At a room temperature, this polymer indicated a state of its being tough and transparent glass. Further, its 10%
thermal decomposition temperature was 462C, which indicated that the polymer had high thermal stability.
Furthermore, this polymer had colorless transparency, a low refractive index of 1.34, and a high light transmission factor of 95~.
The gas permeability coefficient of this polymer to various gasses was measured, the results of the measurement being shown in the following Table.
13~2638 Gas Permeation Coefflcient (cm3cm/cm2sec. cmHg) He106 x lO lO
H226 x lO lO
C2 8.2 x lO-l 23 9 x lO-l N2 0.81 x lO lO
CH4 0.21 x lO lO
EXAMPLE 2 "
10 g of PAVE, lO g of trichlorotrifluoroethane (hereinafter abbreviated as "R-113~), and lO mg of diisopropylperoxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass.
After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 14 hours at 40C. The pressure during the polymerization was lower than the atmospheric pressure.
As the result, there was obtained 6.1 g of a polymer.
The intrinsic viscosity of this polymer [~ ] was 0.37 at 30C in "FC-75", hence the resulted polymer was found to have a high molecular weight. It was also disco,vered from the l9F-NMR spectrum measurement that the polymer was similar to that obtained in Example 1 above.
~1302638 EXAI'IPLE 3 30 g of PAVE and 10 mg of the polymerization initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 30C. The pressure during the polymerization was lower than the atmospheric pressure.
After the polymerization reaction, there was obtained 16 g of a polymer.
The intrinsic viscosity of this polymer [~ ] was 0.505 at 30 C in "FC-75".
(Synthesis of CF2=CFCF2CF2OCF=CF2) 2,000 g of CF2ClCFClCF2COF was reacted with hexafluoropropyleneoxide in the presence of cesium fluoride, and was further converted into potassium salt thereof by use of potassium hydroxide, after which the substance was subjected to thermal decomposition, thereby obtaining CF2ClCFClCF2CF2OCF=CF2 as the product.
Subsequently, this product was reacted with a mixture of Zn and dioxane to carry out dechlorination, thereby obtaining 300 g of CF2=CFCF2CF2OCF=CF2 (PBVE) having boiling point of 64C. The structure of this fluorine-containing monomer was verified by measurèment of 19F-NMR spectrum.
130:~638 E~AMPLE 4 5.42 g of PBVE as obtained in the above-described Example of Synthesis l and 10 mg of the polymerization o initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After the degassing under freezing condition was repeated for two times, the polymerization reaction was conducted for 48 hours at 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. From this polymerization reaction, there was obtained 2.22 g of a polymer.
When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm 1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its l9F-NMR spectrum was measured, there was obtained a spectrum which indicated the following repeating structure.
~CF2 --tCF2 fF CF~- or ~CF2-CF-CF-CF2) The intrinsic viscosity of this polymer [ n ] was 0.55 at 30C in "FC-75", which indicated that this polymer had ~30:~638 a high degree of polymerization.
The glass transition temperature of this polymer was 108C. At a room temperature, this polymer indicated at state of its being tough and transparent glass. Also, it had 10% thermal decomposition temperature of 457C, thus indicating its high thermal stability. By the way, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as high as 95%, 5 g of PAVE, 5 g of PBVE and lO mg of the o polymerization initiator (C3F7CO)2 were placed in a glass reactor having an inner volume of 60 ml. After the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25C, while agitating the reactants. The pressure during the polymerization reaction as lower than the atmospheric pressure. As the result, there was obtained 5.5 g of a Plymer.
When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm l to be derived from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene and its 19F_NMR spectrum was measured to verify its structure. As the result, the obtained ~302638 polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
~C 2 \ /CF t and a unit of thè cyclic structure to be derived from PBVE
such as represented by the following formula:
~ F2 \ -~CF2-fF-fF-CF2~~;
15C~2 \ /
and containing therein 54% by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer was found to have its intrinsic viscosity [~ ] of 0.44 at 30C in "FC-75", hence high degree of polymerization.
The glass transition point of this polymer was 91C
and indicated a state of its being tough and transparent glass at a room temperature. Further, its 10% thermal decomposition temperature was 435C, thus indicating that the polymer had high thermal stability. Furthermore, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as~high as 95%.
i302638 E~AMPLE 6 5 g of PAVE, 15 g of "R-113", and 80 mg of 5 wt~
solution of the polymerization initiator (C3F7~0)2 were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for three times, O.S g of CF2=CF2 was charged into the reaction system. While shaking the ampoule in an incubator, the polymerization was conducted for six hours at 30C, as the result of which a solid substance was obtained in quantity of 1.5 g .
The thus obtained solid substance was dissolved in perfluorobenzene, and its structure was verified by measurement of 19F-NMR spectrum, from which it was found that the resulted polymer was a copolymer consisting of:
a unit of the cyclic structure to be derived from PAVE
as represented by the following formula:
/CF ~
(CF2-C~ / CF) and a unit of the structure to be derived from CF2=CF2 as represented by the following formula:
(CF2-CF2) and containing therein 81~ by weight of the unit of the cyclic structure to be derived from PAVE. Also, this polymer had its intrinsic~viscosity [~ ] of 0.425 at 30C
~302638 in "FC-75".
20 g of PBVE obtained in Example of Synthesis 1 and 40 mg of the polymerization inltiator (C3F7~0)2 were placed in an ampoule having an inner volume oE 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 1.0 g of CF2=CFCl was charged into the reaction system.
While shaking the ampoule in an incubator, the polymerization reaction was conducted for 10 hours at 25C. As the result, there was obtained a polymer in a quantity of 4.5 g.
Upon measurement of the infrared ray absorption spectrum of this polymer, it was found that there was no absorption in the vicinity of 1790 cm 1 due to the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved into perfluorobenzene, and its structure was verified by measurement of the 19F-NMR spectrum. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula:
C Fz ~ C F 2 - C F-C F - C
C F2 - C F C F ~ or O C F2 o C ~2 i302638 and a unit of the structure to be derived from CF2=CFCl as represented by the following formula.
~ CF2-CFCl~;
and containing therein 84% by weight of the unit of the cyclic structure to be derived from PBVE. This polymer had its intrinsic viscosity of 0.43 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer was in a state of its being tough and transparent glass at a room temperature. It had also a 10% thermal decomposition temperature of 421C, which showed that it had high thermal stability. Further, the polymer showed its solubility in a mixed solution of "FC-75" and "R-113".
20 g of PBVE obtained in Example of Synthesis 1 above and 20 mg of the polymerization initiator (C3F7~0)2 were placed in an ampoule having an inner volume of 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 0.5 g of CF2=CF2 was charged in the reaction system. While shaking this ampoule in an incubator, the polymerization reaction was conducted for five hours at a temperature of 25C. As the result, there was obtained ; 5.8 g of a polymer.
Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinit~ of 1790 cm 1 to be derived ~30;2~38 from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the result of this, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula:
~CF2 (CF2-lCF ÇF~-- or (CF2-CF-CF-CF2~--;
\ /1F2 \ /
. CF2 and a unit of the structure to be derived from CF2=CF2 as represented by the following formula:
~ CF2 -CF2~
and containing therein 94~ by weight of the unit of the cyclic structure to be derived from PBVE. Further, this polymer had its intrinsic viscosity [~ ] of 0.53 in "FC-75" at 30C, thus indicating that it had high degree ` of polymerization. It also indicated a state of its being a tough and transparent polymer at a room temperature.
9 g Of PAVE, 1 g of CF2=CF-O-CF CF CF COOCH and 10 mg of the polymerization initiator (C3F7CO) 2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 24 hours at a temperature of 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained 3.55 g of a polymer.
This polymer was dissolved in perfluorobenzene to measure its 19F-NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
fF~
(CF2-CF ,CF~- and \O-C/F2 a u~t of the structure of the formula:
(CF2-CF~--~ CF2 CF 2 CF 2COOH3, and containing therein 93~ by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer had its intrinsic viscosity [ ~ ] of 0.32 in "FC-75l- at 30C, thus indicating that it had a high degree of polymerization.
The polymer had its glass transition point of 64C, and indicated a state of its being tough and transparent glass. Also, its 10% thermal decomposition temperature i3~2~38 was 430C, thus indicating that it had high thermal stability. Further, this polymer was colorless transparent.
40 g of PAVE~ 5 g of CF2=CF-O-cF2cF2cF2coocH3, and lO
mg of diisopropyl peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass.
After repetition of the degassing under freezing condition for two times, 5 g of CF2=CF2 was charged into the reaction system. While shaking this ampoule in an incubator, the polymerization was conducted for 72 hours at a temperature of 30C. As the result, there was obtained 11.8 g of a polymer.
This polymer was dissolved in perflurobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as 20 represented by the following formula:
\b-C/F2 and units of the formulaS:
(C 2 fF~-- and (CF2CF2~';
OCF2CF2CF2COOcH3 derived from CF2=CF-O-CF2~CF2CF2COOCH3 and CF2=CF2, respectively, and containing therein 82% by weight of the unit of the cyclic structure to be derived from PAVE.
This polymer had its intrinsic viscosity ~ n ] of 0.42 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer was found to have its glass transition point of 58C, and indicated a state of its being tough and transparent polymer at a room temperature. Further, its 10% thermal decGmposition temperature was 421C, thus indicating that it had high thermal stability.
Furthermore, the polymer was colorless transparent.
8 g of PBVE, 1 g of CF2=CFOCF2CF(CF3)OCF2CF2SO2F and 10 mg of the polymerization initiator (C3F7C0)2 were palced in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the consequence, there was obtained 3.8 g of a polymer. This polymer was dissolved in perfluorobenzene to measure its 19F-NMR
spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure i302638 to be derived from PBVE such as represented by the following formula:
/ ~CF~ or (CF2-CF-C\F-CF2~- ;
\ / 2 \C /
and a unit of the structure to be derived from CF2=CFOCF2CF(CF3)OCF2CF2SO2F as represented by the following formula:
~CF2-CF ~
~ ) 'F2CFOCF2CF2SO2F ;
and containing therein 94~ by weight of the unit of the structure to be derived from PBVE.
It was found that this polymer had its intrinsic viscosity [ n ] of 0.38 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer had its glass transition point of 92C, and indicated a state of its being tough and transparent glass. The polymer was colorless transparent. The adhesive property of this polymer with glass was satisfactory.
:;
13026~8 E~AMPLE 12 8 g of PAVE, 2 g of CF2=CF-O-CF2CF2CF3, and lO mg oE
the polymerization initiator (C3F7CO)2 were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was coducted for 24 hours at a temperature of 25~C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained a polymer in a quantity of 1.85 g.
This polymer was dissolved in perfluorobenzene to measure its l9F-NMR spectrum, from which its structure was verified. As the consequence, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula:
C~CF2~
20 2 --~CF2- /CF~- ; and a unit of the structure to be derived from CF2=CF-O-CF2CF2CF3 as represented by the following formula:
~CF2-fF2~
, and containin~ therein 89% by weight of the unit of the cyclic structure to be de~ived from PAVE.
1~02638 It was further found that this polymer had its intrinsic viscosity [~ ] of 0.35 in "FC-75" at 30C, thus indicating that it had high degree of polymerization.
The polymer had its glass transition point of 61C, and indicated a state of its being tough and transparent glass. Furtnermore, its 10~ thermal decomposition temperature was 415C, thus indicating that the polymer had high thermal stability. Moreover, this polymer was colorless transparent, and showed its elongation of 250 at 25C.
The fluorine-containing thermoplastic resinous polymer according to the present invention, containing therein the ether bond in its main chain which has not so far been known, can be readily subjected to press-molding, extrusion-molding, and injection-molding, and, when the polymer is molded into optical parts such as lenses, it exhibits remarkable effect such that the molded article is excellent in its transparency, with added superiority in its chemical-resistant property, electrical insulation, heat-stability, strong acid resistant property, strong alkali resistant property, water-resistant property, moisture-resistant property, and so forth. Further, the polymer according to the present invention possesses high transmiss~bility to the ultraviolet rays, which provides a remarkable effect such that it can substitute various sorts of optical parts i302638 made of quartz glass. Furthermore, since it has high transmissibility to the infrared rays, it can be effectively empolyed for various sorts of infrared ray sensors. Also, the polymer according to the present invention has a low refractive index, in account of which it exhibits an effect such that, when this polymer is prepared into a solution and coated on the surface of the optical parts such as lenses, the light reflection can be reduced. Moreover, the resinous polymer according to the present invention is recognized to be effectively and suitably applicable as the cladding materiai for the optical fibers, material for opto-magnetic discs, p~otective membranes for the solar batteries, gas-separating membranes, protective films for transparent resins such as acrylic resin, polycarbonate resin, and diethylene glycol-bis-(allylcarbonate) resin, etc., and treatment agent for textile materials.
Claims (5)
1. A fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2), said polymer having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
and/or (where: n is an integer of 1 or 2), said polymer having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
2. A polymer according to Claim 1, wherein said group (a) of the repeating units is derived from perfluoroallyl vinyl ether and/or perfluorobutenyl vinyl ether.
3. A fluorine-containing thermoplastic resinous polymer which consists essentially of:
i) a group (a) of repeating units to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2); and ii) a group (b) of repeating units to be represented by the following general formula:
?CF2-CFX?
(where: X is selected from fluorine, chlorine O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) said polymer containing therein at least 80% by weight of the group of repeating units (a), and having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
i) a group (a) of repeating units to be represented by the following general formula:
and/or (where: n is an integer of 1 or 2); and ii) a group (b) of repeating units to be represented by the following general formula:
?CF2-CFX?
(where: X is selected from fluorine, chlorine O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3) said polymer containing therein at least 80% by weight of the group of repeating units (a), and having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.
4. A polymer according to Claim 3, wherein said group (a) of the repeating units is derived from perfluoroallyl vinyl ether and/or perfluorobutenyl vinyl ether.
5. A polymer according to Claim 3 or 4, wherein said group (b) of repeating units is derived from a comonomer to be represented by the following general formula:
CF2=CFX
(where: X is selected from fluorine, chlorine, O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3)
CF2=CFX
(where: X is selected from fluorine, chlorine, O-CF2CF2CF3, O-CF2CF(CF3)OCF2CF2SO2F, and O-CF2CF2CF2COOCH3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20186487 | 1987-08-14 | ||
| JP201864/1987 | 1987-08-14 |
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|---|---|
| CA1302638C true CA1302638C (en) | 1992-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000574687A Expired - Lifetime CA1302638C (en) | 1987-08-14 | 1988-08-12 | Fluorine-containing cyclic polymer |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4897457A (en) |
| EP (2) | EP0303298B1 (en) |
| KR (1) | KR930007505B1 (en) |
| CA (1) | CA1302638C (en) |
| DE (2) | DE3889805T2 (en) |
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| US3114778A (en) * | 1963-12-17 | Fluorinated vinyl ethers and their | ||
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| US3418302A (en) * | 1963-08-30 | 1968-12-24 | Du Pont | Perfluorocyclic ether polymers |
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-
1988
- 1988-08-10 US US07/233,820 patent/US4897457A/en not_active Expired - Lifetime
- 1988-08-10 US US07/233,821 patent/US4910276A/en not_active Expired - Lifetime
- 1988-08-12 DE DE3889805T patent/DE3889805T2/en not_active Expired - Lifetime
- 1988-08-12 DE DE88113179T patent/DE3881119T2/en not_active Expired - Lifetime
- 1988-08-12 EP EP88113179A patent/EP0303298B1/en not_active Expired - Lifetime
- 1988-08-12 EP EP88113167A patent/EP0303292B1/en not_active Expired - Lifetime
- 1988-08-12 CA CA000574687A patent/CA1302638C/en not_active Expired - Lifetime
- 1988-08-13 KR KR1019880010363A patent/KR930007505B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0303292A3 (en) | 1990-04-25 |
| KR890003812A (en) | 1989-04-18 |
| EP0303292A2 (en) | 1989-02-15 |
| DE3889805T2 (en) | 1995-01-12 |
| EP0303298A2 (en) | 1989-02-15 |
| EP0303298B1 (en) | 1993-05-19 |
| KR930007505B1 (en) | 1993-08-12 |
| US4910276A (en) | 1990-03-20 |
| DE3881119D1 (en) | 1993-06-24 |
| EP0303298A3 (en) | 1990-05-02 |
| DE3889805D1 (en) | 1994-07-07 |
| EP0303292B1 (en) | 1994-06-01 |
| US4897457A (en) | 1990-01-30 |
| DE3881119T2 (en) | 1993-12-16 |
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