CA2147045A1 - Copolymers of tetrafluoroethylene, hexafluoropropylene and ethylene - Google Patents
Copolymers of tetrafluoroethylene, hexafluoropropylene and ethyleneInfo
- Publication number
- CA2147045A1 CA2147045A1 CA002147045A CA2147045A CA2147045A1 CA 2147045 A1 CA2147045 A1 CA 2147045A1 CA 002147045 A CA002147045 A CA 002147045A CA 2147045 A CA2147045 A CA 2147045A CA 2147045 A1 CA2147045 A1 CA 2147045A1
- Authority
- CA
- Canada
- Prior art keywords
- mol
- copolymer
- units
- copolymers
- ethylene
- 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.)
- Abandoned
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005977 Ethylene Substances 0.000 title claims abstract description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013022 venting Methods 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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Abstract
Copolymers, containing from 45 to 55 mol % of units of tetrafluoroethylene, from 10 to 20 mol % of units of hexafluoropropylene and from 25 to 40 mol % of units of ethylene and having a melting point of from about 140 to about 170°C can be processed from the melt. They are suitable as coatings for temperature-sensitive substrates.
Description
70~5 HOECHST AKTIENGESELLSCHAFT HOE 94/F 910 Dr.KL-nu Werk Gendorf Copolymers of tetrafluoroethylene, hexafluoropropylene and ethylene Description The invention relates to copolymers containing from 45 to 55 mol % of units of tetrafluoroethylene (TFE), from 10 to 20 mol % of units of hexafluoropropylene (HFP) and from 25 to 40 mol % of units of ethylene (ET) and having a melting point in the range from about 140 to about 170C. The presence of subordinate amounts of further comonomers compatible with the specified monomers is not excluded.
Preferred copolymers contain from 48 to 55 mol % of TFE, from 11 to 18 mol % of HFP and from 27 to 39 mol %, in particular from 29 to 38 mol %, of ET.
On a weight basis, the copolymers of the invention contain from about 53 to 6g % of TFE, from about 18 to 36 % of HFP and from about 7 to 15 % of ET.
The polymers of the invention are distinguished by their relatively low melting point. They are therefore suitable for processing from the melt together with substrates which cannot withstand relatively high temperatures, such as fiber material or temperature-sensitive plastics.
Terpolymers of TFE, HFP and ET have been known for a long time: US-A 3 817 951 describes terpolymers composed of, (in mol percent) from 40 to 60 % of ET, from 20 to 30 %
of TFE and from 10 to 30 % of HFP. Reference is expressly made to the fact that the advantageous properties of these terpolymers are achieved only within this critical narrow range of the specified proportions. Corresponding to the low TFE content, the terpolymers mentioned in the examples contain 46 or 50 mol % of ET.
US-A 4 338 237 relates to a process for preparing stable aqueous colloidal dispersions of copolymers, including terpolymers of TFE, HFP and ET. The TFE content is from 30 to 60 mol %, the HFP content is from 0 to 15 mol % and the ET content is from 40 to 60 mol %. The terpolymers of these monomers mentioned in the examples contain 4.5 or 4.7 mol % of HFP and correspondingly 46.5 or 46.8 mol %
of ET. The concentrated dispersions are suitable for impregnating or coating fiber materials and surfaces and the coagulated dispersions can be worked up to give melt granules. In this form, the copolymers can then be processed from the melt.
EP-B 92 675 discloses sheathing materials for optical fibers, with a copolymer containing from 30 to 60 mol %
of ethylene, from 20 to 69 mol % of TFE or chlorotri-fluoroethylene and from 1 to 30 % of a further olefin, which can be HFP, being used. The Example 1 relates to a terpolymer containing 55 mol % of ET, 25 mol % of TFE and 20 mol % of HFP; the Comparative Example 3 relates to a terpolymer containing 70 mol % of ET, 23 mol % of TFE and 7 mol % of HFP.
The preparation of the copolymers of the invention can be carried out in a manner known per se, as is also described in the abovementioned documents. The copolymerization is preferably carried out in aqueous medium, if desired using a low-molecular-weight hydrocar-bon as chain transfer agent, and a redox system as initiator.
The copolymers of the invention have a high resistance to aggressive media. In conjunction with the relatively low melting point they are therefore suitable for coating or lining shaped articles which cannot withstand high temperatures. For this purpose, for example, the copolymers can be first processed into a film which is then welded to the substrate, if desired with the aid of a suitable binder.
2t4704S
The invention is illustrated in the following examples.
Percentages are by weight, unless otherwise indicated.
Example 1 An internally enamelled polymerization reactor having a total volume of 195 l, provided with an impeller stirrer, is charged with 120 1 of deionized water, and 500 g of ammonium perfluorooctanoate (in the form of 1667 g of a 30 % strength solution in water, commercial product of the 3M company), 242 g of diammonium oxalate monohydrate and 69 g of oxalic acid monohydrate are dissolved there-in. After sealing the reactor, it is first flushed five times with nitrogen and subsequently once with 1 bar of TFE.
After depressurization and heating to 43C, 10 g of n-pentane and 9 kg of HFP are pumped in via a line under moderate stirring. The stirring is then increased to 210 rpm and 2.05 kg of TFE and 133 g of ET are fed into the reactor via the gas phase, so that a total pressure of 17 bar is achieved.
The polymerization is then initiated by pumping in a solution of 5 g of potassium permanganate in 250 ml of water and maintained by continuously feeding in 14 g of potassium permanganate, dissolved in 0.7 l of water, per hour. The total monomer pressure of 17 bar is automati-cally maintained by continuous feeding in of a mixturehaving a molar ratio of TFE : ET : HFP = 2.3 : 1.7 : 1.
The reaction is stopped at a copolymer solids content, based on aqueous reaction medium used, of about 21 % by venting of the monomer mixture.
The dispersion is then coagulated by means of the rapidly running stirrer. The precipitated copolymer solid is separated off from the liquor, washed a number of times with water, dried in a nitrogen atmosphere for 15 hours ~ 21~7045 at 110C and subsequently melt granulated.
The polymer composition and further characteristic data are summarized in the table below.
Examples 2 to 5 The Exampleæ 2 to 5 are carried out using a similar method to Example 1. Alterations, for example to the metering in of como~omer, are given together with the polymer propertieæ in the table below.
Table 1 0 Example No. 1 2 3 4 5 Polymerization temperature [C] 43.041.0 45.0 49.0 42.0 TFE: Total amount [kg] 20.3515.68 15.33 13.40 20.40 of this, initially charged[kg] 2.05 2.18 1.831.27 2.10 of this, subsequently metered in [kg]18.3013.5013.50 12.13 18.30 HFP: Total amount [kg]20.8816.3318.20 19.07 20.88 of this, initially charged [kg]9.0o 8.61 9.50 10.50 9.00 of this, subsequently metered in [kg]11.887.728.70 8.57 11.88 ET: Total amount [kg] 3.82 2.85 2.24 1.843.79 of this, initially charged[kg] 0.13 0.1490.0870.070 0.133 of this, subsequently metered in [kg] 3.69 2.70 2.16 1.77 3 66 n-pentane [g] 10.00 15.00 --- --- 20.00 KMnO4 [g] 66.00 50.00 51.00 75.00 66.00 Polymerization time [h] 5.00 3.30 2.80 4.20 5.00 Polymer solids content [~] 20.50 15.10 15.30 15.40 20.10 MFI 5 kg/297C [g/10 min] 7 21 0.6 17.8 57.0 Mp by DSC [C] 155 169 152 140 159 Fluorine content [~] 65.9 65.9 68.2 68.8 65.9 Product composition : TFE [mol-~] 48.7350.5754.05 52.49 49.44 (NMR) HFP [mol-~] 13.5111.9414.8017.8712.91 8T [mol-~] 37.7637.4931.1529.6437.66 MFI: Melt flow index at 297C and 5 kg load, in accord-ance with D~N 53 735/ASTM D 3159.
Preferred copolymers contain from 48 to 55 mol % of TFE, from 11 to 18 mol % of HFP and from 27 to 39 mol %, in particular from 29 to 38 mol %, of ET.
On a weight basis, the copolymers of the invention contain from about 53 to 6g % of TFE, from about 18 to 36 % of HFP and from about 7 to 15 % of ET.
The polymers of the invention are distinguished by their relatively low melting point. They are therefore suitable for processing from the melt together with substrates which cannot withstand relatively high temperatures, such as fiber material or temperature-sensitive plastics.
Terpolymers of TFE, HFP and ET have been known for a long time: US-A 3 817 951 describes terpolymers composed of, (in mol percent) from 40 to 60 % of ET, from 20 to 30 %
of TFE and from 10 to 30 % of HFP. Reference is expressly made to the fact that the advantageous properties of these terpolymers are achieved only within this critical narrow range of the specified proportions. Corresponding to the low TFE content, the terpolymers mentioned in the examples contain 46 or 50 mol % of ET.
US-A 4 338 237 relates to a process for preparing stable aqueous colloidal dispersions of copolymers, including terpolymers of TFE, HFP and ET. The TFE content is from 30 to 60 mol %, the HFP content is from 0 to 15 mol % and the ET content is from 40 to 60 mol %. The terpolymers of these monomers mentioned in the examples contain 4.5 or 4.7 mol % of HFP and correspondingly 46.5 or 46.8 mol %
of ET. The concentrated dispersions are suitable for impregnating or coating fiber materials and surfaces and the coagulated dispersions can be worked up to give melt granules. In this form, the copolymers can then be processed from the melt.
EP-B 92 675 discloses sheathing materials for optical fibers, with a copolymer containing from 30 to 60 mol %
of ethylene, from 20 to 69 mol % of TFE or chlorotri-fluoroethylene and from 1 to 30 % of a further olefin, which can be HFP, being used. The Example 1 relates to a terpolymer containing 55 mol % of ET, 25 mol % of TFE and 20 mol % of HFP; the Comparative Example 3 relates to a terpolymer containing 70 mol % of ET, 23 mol % of TFE and 7 mol % of HFP.
The preparation of the copolymers of the invention can be carried out in a manner known per se, as is also described in the abovementioned documents. The copolymerization is preferably carried out in aqueous medium, if desired using a low-molecular-weight hydrocar-bon as chain transfer agent, and a redox system as initiator.
The copolymers of the invention have a high resistance to aggressive media. In conjunction with the relatively low melting point they are therefore suitable for coating or lining shaped articles which cannot withstand high temperatures. For this purpose, for example, the copolymers can be first processed into a film which is then welded to the substrate, if desired with the aid of a suitable binder.
2t4704S
The invention is illustrated in the following examples.
Percentages are by weight, unless otherwise indicated.
Example 1 An internally enamelled polymerization reactor having a total volume of 195 l, provided with an impeller stirrer, is charged with 120 1 of deionized water, and 500 g of ammonium perfluorooctanoate (in the form of 1667 g of a 30 % strength solution in water, commercial product of the 3M company), 242 g of diammonium oxalate monohydrate and 69 g of oxalic acid monohydrate are dissolved there-in. After sealing the reactor, it is first flushed five times with nitrogen and subsequently once with 1 bar of TFE.
After depressurization and heating to 43C, 10 g of n-pentane and 9 kg of HFP are pumped in via a line under moderate stirring. The stirring is then increased to 210 rpm and 2.05 kg of TFE and 133 g of ET are fed into the reactor via the gas phase, so that a total pressure of 17 bar is achieved.
The polymerization is then initiated by pumping in a solution of 5 g of potassium permanganate in 250 ml of water and maintained by continuously feeding in 14 g of potassium permanganate, dissolved in 0.7 l of water, per hour. The total monomer pressure of 17 bar is automati-cally maintained by continuous feeding in of a mixturehaving a molar ratio of TFE : ET : HFP = 2.3 : 1.7 : 1.
The reaction is stopped at a copolymer solids content, based on aqueous reaction medium used, of about 21 % by venting of the monomer mixture.
The dispersion is then coagulated by means of the rapidly running stirrer. The precipitated copolymer solid is separated off from the liquor, washed a number of times with water, dried in a nitrogen atmosphere for 15 hours ~ 21~7045 at 110C and subsequently melt granulated.
The polymer composition and further characteristic data are summarized in the table below.
Examples 2 to 5 The Exampleæ 2 to 5 are carried out using a similar method to Example 1. Alterations, for example to the metering in of como~omer, are given together with the polymer propertieæ in the table below.
Table 1 0 Example No. 1 2 3 4 5 Polymerization temperature [C] 43.041.0 45.0 49.0 42.0 TFE: Total amount [kg] 20.3515.68 15.33 13.40 20.40 of this, initially charged[kg] 2.05 2.18 1.831.27 2.10 of this, subsequently metered in [kg]18.3013.5013.50 12.13 18.30 HFP: Total amount [kg]20.8816.3318.20 19.07 20.88 of this, initially charged [kg]9.0o 8.61 9.50 10.50 9.00 of this, subsequently metered in [kg]11.887.728.70 8.57 11.88 ET: Total amount [kg] 3.82 2.85 2.24 1.843.79 of this, initially charged[kg] 0.13 0.1490.0870.070 0.133 of this, subsequently metered in [kg] 3.69 2.70 2.16 1.77 3 66 n-pentane [g] 10.00 15.00 --- --- 20.00 KMnO4 [g] 66.00 50.00 51.00 75.00 66.00 Polymerization time [h] 5.00 3.30 2.80 4.20 5.00 Polymer solids content [~] 20.50 15.10 15.30 15.40 20.10 MFI 5 kg/297C [g/10 min] 7 21 0.6 17.8 57.0 Mp by DSC [C] 155 169 152 140 159 Fluorine content [~] 65.9 65.9 68.2 68.8 65.9 Product composition : TFE [mol-~] 48.7350.5754.05 52.49 49.44 (NMR) HFP [mol-~] 13.5111.9414.8017.8712.91 8T [mol-~] 37.7637.4931.1529.6437.66 MFI: Melt flow index at 297C and 5 kg load, in accord-ance with D~N 53 735/ASTM D 3159.
Claims (12)
- Patent Claims l. A copolymer containing from 45 to 55 mol % of units of tetrafluoroethylene, from 10 to 20 mol % of units of hexafluoropropylene and from 25 to 40 mol % of units of ethylene and having a melting point in the range from about 140 to about 170°C.
- 2. A copolymer as claimed in claim 1, containing from 48 to 55 mol % of units of tetrafluoroethylene, from 11 to 18 mol % of units of hexafluoropropylene and from 27 to 39 mol % of units of ethylene.
- 3. A copolymer as claimed in claim 2, containing from 29 to 38 mol % of units of ethylene.
- 4. A substrate coated with a copolymer as claimed in claim 1.
- 5. A substrate coated with a copolymer as claimed in claim 2.
- 6. A substrate coated with a copolymer as claimed in claim 3.
- 7. A process for coating a temperature-sensitive substrate, which comprises contacting the said substrate with a melt of a copolymer as claimed in claim 1.
- 8. A process for coating a temperature-sensitive substrate, which comprises contacting the said substrate with a melt of a copolymer as claimed in claim 2.
- 9. A process for coating a temperature-sensitive substrate, which comprises contacting the said substrate with a melt of a copolymer as claimed in claim 3.
- 10. A film consisting essentially of a copolymer as claimed in claim 1.
- 11. A film consisting essentially of a copolymer as claimed in claim 2.
- 12. A film consisting essentially of a copolymer as claimed in claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4412789.8 | 1994-04-14 | ||
| DE4412789A DE4412789A1 (en) | 1994-04-14 | 1994-04-14 | Copolymers of tetrafluoroethylene, hexafluoropropylene and ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2147045A1 true CA2147045A1 (en) | 1995-10-15 |
Family
ID=6515334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002147045A Abandoned CA2147045A1 (en) | 1994-04-14 | 1995-04-13 | Copolymers of tetrafluoroethylene, hexafluoropropylene and ethylene |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0677538B1 (en) |
| JP (1) | JP3609866B2 (en) |
| KR (1) | KR100348913B1 (en) |
| CN (1) | CN1089770C (en) |
| BR (1) | BR9501574A (en) |
| CA (1) | CA2147045A1 (en) |
| DE (2) | DE4412789A1 (en) |
| PL (1) | PL182014B1 (en) |
| RU (1) | RU2159780C2 (en) |
| TW (1) | TW337524B (en) |
| ZA (1) | ZA953054B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6380313B1 (en) | 2000-06-27 | 2002-04-30 | Dyneon Llc | Polymer processing additive containing a perfluorovinylether-modified flouropolymer and a melt processable thermoplastic polymer composition employing the same |
| US6482522B1 (en) | 1997-12-19 | 2002-11-19 | Dyneon Llc | Elastomer compositions for bonding to fluoropolymers |
| US6489420B1 (en) | 2000-06-27 | 2002-12-03 | Dyneon Llc | Fluoropolymers with improved characteristics |
| US7662765B2 (en) | 2004-02-17 | 2010-02-16 | Optimer, Inc. | Compositions useful as fabric softener |
| US9982812B2 (en) | 2014-03-10 | 2018-05-29 | Saint-Gobain Performance Plastics Corporation | Multilayer flexible tube and methods for making same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372870B1 (en) | 1997-06-23 | 2002-04-16 | Daikin Industries Ltd. | Tetrafluoroethylene copolymer and use thereof |
| JPH11315121A (en) | 1998-05-01 | 1999-11-16 | Daikin Ind Ltd | Functional group-containing fluorine-containing copolymer |
| ATE344805T1 (en) | 1999-09-08 | 2006-11-15 | Daikin Ind Ltd | FLUORCHEMICAL ADHESIVE MATERIAL AND LAYERED PRODUCT OBTAINED THEREFROM |
| CA2610272A1 (en) | 2005-06-14 | 2006-12-21 | Asahi Glass Company, Limited | Multilayer laminate of fluororesin |
| CN102532388B (en) * | 2011-12-31 | 2014-08-20 | 中昊晨光化工研究院 | Method for preparing ethylene-tetrafluoroethylene copolymers |
| CN110467698B (en) * | 2018-05-10 | 2020-10-09 | 中昊晨光化工研究院有限公司 | Ethylene modified fluorinated ethylene propylene resin and preparation method thereof |
| CN110272609A (en) * | 2019-06-18 | 2019-09-24 | 南通展鹏塑料有限公司 | A kind of ABS plastic and preparation method thereof of anti-aging color inhibition |
| WO2021054363A1 (en) * | 2019-09-20 | 2021-03-25 | ダイキン工業株式会社 | Fluorine-containing copolymer |
| JP6870794B1 (en) * | 2020-02-07 | 2021-05-12 | ダイキン工業株式会社 | Copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3512633A1 (en) * | 1985-04-06 | 1986-10-09 | Hoechst Ag, 6230 Frankfurt | STABLE, AQUEOUS COLLOIDAL DISPERSIONS OF TYPE TETRAFLUORETHYLENE ETHYLENE COPOLYMERISATS AND METHOD FOR THE PRODUCTION THEREOF |
-
1994
- 1994-04-14 DE DE4412789A patent/DE4412789A1/en not_active Withdrawn
-
1995
- 1995-02-21 TW TW084101587A patent/TW337524B/en active
- 1995-04-08 EP EP95105347A patent/EP0677538B1/en not_active Expired - Lifetime
- 1995-04-08 DE DE59500661T patent/DE59500661D1/en not_active Expired - Fee Related
- 1995-04-12 KR KR1019950008451A patent/KR100348913B1/en not_active IP Right Cessation
- 1995-04-12 JP JP08725495A patent/JP3609866B2/en not_active Expired - Fee Related
- 1995-04-12 PL PL95308105A patent/PL182014B1/en not_active IP Right Cessation
- 1995-04-13 RU RU95105797/04A patent/RU2159780C2/en not_active IP Right Cessation
- 1995-04-13 CA CA002147045A patent/CA2147045A1/en not_active Abandoned
- 1995-04-13 BR BR9501574A patent/BR9501574A/en not_active Application Discontinuation
- 1995-04-13 CN CN95104216A patent/CN1089770C/en not_active Expired - Fee Related
- 1995-04-13 ZA ZA953054A patent/ZA953054B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482522B1 (en) | 1997-12-19 | 2002-11-19 | Dyneon Llc | Elastomer compositions for bonding to fluoropolymers |
| US6833043B1 (en) | 1997-12-19 | 2004-12-21 | 3M Innovative Properties Company | Elastomer compositions for bonding to fluoropolymers |
| US6380313B1 (en) | 2000-06-27 | 2002-04-30 | Dyneon Llc | Polymer processing additive containing a perfluorovinylether-modified flouropolymer and a melt processable thermoplastic polymer composition employing the same |
| US6489420B1 (en) | 2000-06-27 | 2002-12-03 | Dyneon Llc | Fluoropolymers with improved characteristics |
| US6610807B2 (en) | 2000-06-27 | 2003-08-26 | 3M Innovative Properties Company | Fluoropolymers with improved characteristics |
| US7662765B2 (en) | 2004-02-17 | 2010-02-16 | Optimer, Inc. | Compositions useful as fabric softener |
| US9982812B2 (en) | 2014-03-10 | 2018-05-29 | Saint-Gobain Performance Plastics Corporation | Multilayer flexible tube and methods for making same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1112132A (en) | 1995-11-22 |
| KR100348913B1 (en) | 2002-11-11 |
| BR9501574A (en) | 1995-11-14 |
| PL308105A1 (en) | 1995-10-16 |
| DE59500661D1 (en) | 1997-10-23 |
| CN1089770C (en) | 2002-08-28 |
| KR950032333A (en) | 1995-12-20 |
| EP0677538B1 (en) | 1997-09-17 |
| DE4412789A1 (en) | 1995-10-19 |
| ZA953054B (en) | 1996-03-06 |
| EP0677538A1 (en) | 1995-10-18 |
| TW337524B (en) | 1998-08-01 |
| JPH0841131A (en) | 1996-02-13 |
| RU95105797A (en) | 1997-01-10 |
| RU2159780C2 (en) | 2000-11-27 |
| PL182014B1 (en) | 2001-10-31 |
| JP3609866B2 (en) | 2005-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3677989A (en) | Ethylene/acrylic acid copolymer emulsions | |
| JP3519411B2 (en) | Tetrafluoroethylene copolymer | |
| US4262101A (en) | Copolymers of tetrafluoroethylene and process for their manufacture | |
| EP0460936B1 (en) | Methanol copolymerization of ethylene | |
| EP0911347B1 (en) | Copolymers of maleic anhydride or acid and fluorinated olefins | |
| CA2147045A1 (en) | Copolymers of tetrafluoroethylene, hexafluoropropylene and ethylene | |
| EP1432744B2 (en) | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers | |
| CN100371358C (en) | Amorphous fluoropolymer containing perfluoro (ethyl vinyl ether) | |
| CA1215497A (en) | Process for preparing tetrafluoroethylene/fluoro(alkyl vinyl ether) copolymer | |
| CA2041559C (en) | Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same | |
| US5641571A (en) | Polytetrafluoroethylene micor powders, their preparation and use | |
| WO2008079394A1 (en) | Crosslinkable vinyl fluoride copolymers | |
| EP2310430B1 (en) | Melt-flowable fluoropolymer comprising repeating units arising from tetrafluoroethylene and a hydrocarbon monomer having a functional group and a polymerizable carbon-carbon double bond | |
| CN105153603A (en) | Ultra-high molecular weight poly(vinylidene fluoride) and manufacturing method thereof | |
| KR20010100009A (en) | Method for Coating Reactors for High-Pressure Polymerisation of 1-Olefins | |
| WO2001098384A2 (en) | Process for manufacture of a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether) | |
| EP2310429B1 (en) | Non-melt-flowable perfluoropolymer comprising repeating units arising from tetrafluoroethylene and a monomer having a functional group and a polymerizable carbon-carbon double bond | |
| US4053445A (en) | Solutions of ethylene-chlorotrifluoroethylene copolymers | |
| EP0214231B1 (en) | Non-aqueous dispersions of relatively high molecular weight epoxy resins | |
| CA2394062A1 (en) | Perfluoro copolymers of tetrafluoroethylene and perfluoro alkyl vinyl ethers | |
| JPH05271352A (en) | Preparation of melt-processable acrylonitrile/ methacrylonitrile copolymer | |
| CN112812217A (en) | Fluoropolymer with high peeling strength and high transparency and preparation method thereof | |
| RU2164922C2 (en) | Method of preparing of vinylidene fluoride with 5-12 mol % of hexafluoropropylene | |
| EP0721961B1 (en) | Process for producing vinyl ester polymers and process for producing vinyl alcohol polymers | |
| WO2001012688A1 (en) | Melt processable multipolymers of acrylonitrile monomer, halogenated monomers and olefinically unsaturated monomers and the process to make them and products therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |