GB2072203A - Graft polyvinylidene fluoride copolymers - Google Patents
Graft polyvinylidene fluoride copolymers Download PDFInfo
- Publication number
- GB2072203A GB2072203A GB8108888A GB8108888A GB2072203A GB 2072203 A GB2072203 A GB 2072203A GB 8108888 A GB8108888 A GB 8108888A GB 8108888 A GB8108888 A GB 8108888A GB 2072203 A GB2072203 A GB 2072203A
- Authority
- GB
- United Kingdom
- Prior art keywords
- graft
- polyvinylidene fluoride
- copolymer
- pvdf
- metal substrate
- 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.)
- Granted
Links
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 53
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000001632 acidimetric titration Methods 0.000 description 1
- 238000001838 alkalimetric titration Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
Abstract
A graft copolymer suitable for adhering to a metal surface, consisting of a main polymer chain of polyvinylidene fluoride having 2 to 25% by weight of the copolymer of grafts of acrylic acid or methacrylic acid polymer attached thereto. This copolymer is obtained by graft polymerisation on to a polyvinylidene fluoride substrate pre-irradiated at at least 3 x 10<5> rads. The copolymer is particularly recommended for the protection of metals used out of doors
Description
SPECIFICATION
Graft polyvinylidene fluoride copolymers
This invention relates to polyvinylidene fluoride
copolymers, more particularly to copolymers of
polyvinylidene fluoride (PVDF) treated so that,
without any other intermediary, they will adhere
directly to metal surfaces. The invention also
relates to a method of producing such copolymers.
PVDF is known for its resistance to chemical
agents, uitraviolet rays and abrasion. All these
qualities make it an ideal material for use
externally and particularly for protecting metals.
This latter use, however, has not been entirely
satisfactory, owing to the lack of direct adhesion
of PVDF to metals. The only known PVDF-based coatings for metals always require the application
of an intermediate bonding layer between the
metal and the PVDF.
It has been found that the product obtained by
grafting grafts of acrylic acid or methacrylic acid
polymers on to a PVDF main chain not only retains the qualities of PVDF but also has the property of adhering directly to metals without any intermediate adhesive. A graft polymer of this kind
is obtained by graft polymerisation of acrylic or
methacrylic acid on to the macromolecular chain of PVDF. These polyacrylic chains are usually grafted on to a PVDF homopolymer. However, the homopolymer may be replaced by a copolymer containing at least 90% of vinylidene fluoride residues, these copolymers still retaining the properties of the PVDF homopolymer.
Graft polymerisation is known per se. It consists of contacting PVDF having active sites on its main chain with the graft initiating acrylic monomer for 4 to 12 hours at a temperature of from 50 to 800 C. The reaction is usually carried out in the presence of water containing a water-soluble inhibitor such as, for example, CuSO4 or FeSO4, in order to prevent, as far as possible, the formation of acrylic homopolymer which increases the viscosity of the graft polymerisation medium and which has to be separated off and discarded. The graft polymerisation may also be carried out in the presence of a PVDF solvent.In order to obtain a graft polymer having good adhesion to metals and retaining the properties of PVDF, it is recommended to graft to the main PVDF chain at least 2% by weight, of the total weight of graft polymer, of polyacrylic grafts. If grafting conditions are used which result in high levels of grafted methacrylic acid, it is possible to mix this graft product with untreated polymer to obtain solutions which yield adhesive coatings. The high grafting levels, particularly those exceeding 25% by weight of polyacrylic grafts on the main PVDF chain which are obtained with highly irradiated products, are not of much value, since PVDF is greatly degraded by excessive exposure to gamma radiation.
One of the ways of creating active sites on the main polymer chain is to irradiate the PVDF prior to the graft polymerisation. The irradiation of polyvinylidene fluoride is known and is described, in particular, in U.S. Patent No. 4 137 137.
Polyvinylidene fluoride is subjected, in air, to ionising radiation. In practice, this ionising radiation comes from a source of gamma or beta radiation. The dose required to ensure that effective grafting can be carried out is a minimum irradiation of the polyvinylidene fluoride at at least 3 x 105 rads. The polyvinylidene fluoride may be irradiated in the form of the crude polymer or already converted to a greater or lesser extent.
Usually, to obtain maximum accessibility of the active sites, the polyvinylidene fluoride is irradiated in the form of a powder, the particle size of which may vary from 0.2 to 100 , or else in the form of filaments of at least 200 y. After irradition, the polyvinylidene fluoride can immediately be brought into contact with the monomer for the purpose of graft polymerisation, or else stored at a temperature usually below 100C until the grafting is carried out.
The protection of the metals using the graft polymer is effected in the conventional manner customary in coating metal parts with thermoplastics. The coatings may be obtained by hot drying (a suitable temperature being 2000 C) of a solution of graft PVDF in a solvent such as, for example, dimethylformamide, or a plastisol of the same graft PVDF in latent solvents such as dimethyl phthalate, diisobutyl ketone, isophorone, cyclohexanone or mixtures thereof. The coatings may also be obtained by projecting graft PVDF powder on to the metal surface, which has previously been heated to about 280--3800C; a number of applications of graft polymer, alternating with periods in the drying chamber, may be made so as to regulate the thickness of the coating. The coatings obtained adhere particularly well to steel, galvanised steel and aluminium.On this latter metal, the coatings will withstand 70 hours' immersion in water at 1 200C without any apparent degradation.
Before the application of the coating, the metal sheets are preferably subjected to the surface treatments suitable for each metal which are generally carried out before the application of any coating or paint, such treatments include degreasing, sanding and combined treatments with phosphoric and chromic compounds.
The following Examples illustrate the present invention.
EXAMPLE 1
50 9 of polyvinylidene fluoride in powder form obtained from a latex and irradiated at 0.8 Mrad, 93 g of water containing 7 g of methacrylic acid and 0.030 g of dissolved CuSO4. 5H20 are placed in a stirred 500 cm3 container, in a nitrogen atmosphere. The mixture is heated to 600C for 6 hours. The resultant grafted PVDF copolymer is separated by filtration, centrifuged, and washed with water on a filter, and then the product is dried in a drying chamber at 1000C.
54 g of dry polymer are recovered, containing 9.8% of methacrylic acid. The acid content is determined by alkali-metry with a solution of methanolic potash, the graft polymer is dissolved in dimethylformamide, and 25% of water are added to the solution before titration. The end of neutralisation is monitored by means of the pH meter.
EXAMPLE 2
50 g of powdered polyvinylidene fluoride obtained from a latex irradiated at 0.5 Mrad, 100 g of water containing 5 g of methacrylic acid and 0.03 g of dissolved CuS04. 5H2O are placed in the same reactor as in Example 1. The mixture is heated to 850C for 6 hours.
The graft solid is separated by filtration, centrifuged, and washed by redispersing the product in water and filtering it again. It is then dried in the drying chamber at 1200 C.
53.2 g of graft PVDF copolymer are recovered, containing 7.45% of methacrylic acid. The quantity of residual methacrylic acid is determined from the washing waters by acidimetry; 0.74 g of acid are found. By titration of the double bond, 0.72 g of methacrylic acid are found.
EXAMPLE 3
Each of the two graft polymers obtained in
Examples 1 and 2 and the non-irradiated initial polyvinylidene fluoride are put into a 20% by weight solution in dimethylformamide. A fourth solution is also prepared by mixing, in equal amounts by weight. a portion of the solutions of non-irradiated starting polymer and the polymer of
Example 2. Small iron and aluminium plates which have been degreased, scoured with a phosphochromic mixture, rinsed and dried, are covered with these four solutions by steeping, then dried in the oven for T hour at 21 OOC. All the coatings adhere, with the exception of the one containing only the polyvinylidene fluoride, which can be removed from its substrate merely by scratching with a fingernail.
The other six plates are placed in an autoclave half-filled with water, and heated to 1200C for 72 hours. After this treatment, it is impossible even to begin to detach the coating, even by scraping it with a knife blade.
EXAMPLE 4
500 g of polyvinylidene fluoride obtained by suspension polymerisation, in the form of a powder of 40 to 100 y with an apparent density of about 0.7, are placed in a stirred 2 litre reactor under a nitrogen atmosphere. This polyvinylidene fluoride has been irradiated at 1 Mrad. 930 g of water containing 0.3 g of CuS04. 5H2O and 70 g of distilled methacrylic acid are also added. The mixture is heated to 600C for 6 hours.
The graft solid is separated by filtration, centrifuged and washed with water on a filter, then dried in an oven at 1200 C. A graft PVDF copolymer is recovered, having a methacrylic acid content of 12%.
Iron plates, degreased and scoured as before, are heated in an oven to 3000 C, coated by sprinkling with the powdered non-irradiated initial polyvinylidene fluoride and with powdered graft copolymer containing 12% of methacrylic acid. A
number of cycles of sprinkling and placing in the oven are carried out until a coating with a thickness of about 200 u is obtained. Finally, the
plate is placed in the oven for 1 5 minutes and, as
it is taken out of the oven, it is soaked in cold water When scratched with a knife and thus
broken open, the coating of the non-irradiated
initial PVDF pulls away fairly easily, whereas the coating of graft polymer adheres perfectly, even after a period of 72 hours in water at 1000C.
EXAMPLE 5
100 g of PVDF obtained from a latex and irradiated at 1 Mrad, 200 g of water containing
10 g of acrylic acid and 0.05 g of dissolved
CuSO4. 5H20 are placed in the reactor used for
Example 1. The mixture is heated to 830C for 6 hours.
The graft polymer is separated by filtration, centrifuged and washed with water on a filter, and then the product is dried in the oven at 1000C.
101.5 g of dry graft PVDF copolymer are recovered, containing 4.9% of acrylic acid, according to the acidity determination.
As indicated in Example 3, a 20% solution in dimethylformamide is prepared with the graft polymer, and this is used to coat an aluminium plate and a steel plate, which are baked in the oven at 21000 for 15 minutes. This coating of polymer grafted with acrylic acid is found to have the same good resistance to boiling water as the methacrylic acid grafts used in Example 3.
EXAMPLE 6
50 g of powdered polyvinylidene fluoride obtained from a latex and irradiated to 3 Mrads, 75 g of water containing 25 g of methacrylic acid and 0.025 g of dissolved 0uSO4.5H20 are placed in a stirred 500 cm3 container in a nitrogen atmosphere. The mixture is heated to 600C for 6 hours. The graft solid is separated by centrifuging, redispersed in water and centrifuged again, then the product is dried in the oven at 1000C.
62 g of dry graft PVDF copolymer are recovered, containing 24% of methacrylic acid.
1 g of this product is placed with 5 g of pure, non-irradiated PVDF in solution in 30 g of dimethylformamide. Degreased aluminium plates are covered with the solution by soaking, then dried for X hour at 2100C. The same qualities in boiling water are observed as for the other coatings of graft polyvinylidene fluoride used in
Examples 3 and 5.
Claims (9)
1. A graft copolymer suitable for adhering to a metal surface, consisting of a main polymer chain of polyvinylidene fluoride having grafts of acrylic acid or methacrylic acid polymer, the polyacrylic grafts grafted to the main polyvinylidene fluoride chain amounting to from 2 to 25% by weight of the copolymer.
2. A graft copolymer according to Claim 1, substantially as described in any one of the foregoing Examples 1, 2 and 4 to 6.
3. A method of producing a graft polyvinylidene fluoride copolymer, the method comprising graft polymerising an acrylic monomer on to polyvinylidene fluoride which has been irradiated at at least 3 x 105 rads, the grafting being performed so that the weight of the resultant polymer side chains is from 2 to 25% by weight of the copolymer.
4. A method according to Claim 3, substantially as described in any one of the foregoing
Examples 1,2 and 4 to 6.
5. A metal substrate whenever coated with a coating comprising a graft copolymer as claimed in Claim 1 or 2.
6. A metal substrate according to Claim 5, wherein the metal is steel, galvanised steel or aluminium.
7. A metal substrate according to Claim 5 or 6, wherein the coating has been formed from a solution of the graft copolymer in a solvent.
8. A metal substrate according to Claim 5 or 6, wherein the coating has been formed by projecting the graft copolymer onto the surface of the heated metal substrate.
9. A coated metal substrate according to
Claim 5 substantially as described in any one of the foregoing Examples 3 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8006318A FR2478649B1 (en) | 1980-03-21 | 1980-03-21 | VINYLIDENE POLYFLUORIDE TREATED FOR ADHESION ON METALS, PROCESS FOR TREATMENT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2072203A true GB2072203A (en) | 1981-09-30 |
| GB2072203B GB2072203B (en) | 1984-07-25 |
Family
ID=9239936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8108888A Expired GB2072203B (en) | 1980-03-21 | 1981-03-20 | Graft polyvinylidene fluoride copolymers |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS56133309A (en) |
| BE (1) | BE887892A (en) |
| CH (1) | CH647536A5 (en) |
| DE (1) | DE3110384C2 (en) |
| DK (1) | DK156441C (en) |
| FR (1) | FR2478649B1 (en) |
| GB (1) | GB2072203B (en) |
| IT (1) | IT1135264B (en) |
| LU (1) | LU83242A1 (en) |
| NL (1) | NL190930C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990002145A1 (en) * | 1988-08-22 | 1990-03-08 | Commonwealth Scientific And Industrial Research Organisation | Acid treated polyacrylic acid grafted fluorocarbon polymer surface for cell attachment |
| AU608173B2 (en) * | 1988-08-22 | 1991-03-21 | Commonwealth Scientific And Industrial Research Organisation | Acid treated polyacrylic acid grafted fluorocarbon polymer surface for cell attachment |
| GB2309701A (en) * | 1996-01-31 | 1997-08-06 | Aea Technology Plc | Organic electrolyte composition |
| EP0793286A1 (en) * | 1996-01-31 | 1997-09-03 | AEA Technology plc | Grafted polyvinylidene fluoride as a solid polymer electrolyte for eletrochemical cells, and electrochemical cell incorporating same |
| WO1997032347A1 (en) * | 1996-02-27 | 1997-09-04 | Elf Atochem S.A. | Binders for electrodes and their production method |
| WO2006042764A2 (en) * | 2004-10-19 | 2006-04-27 | Arkema France | Coating compositions for inorganic substrates |
| WO2006045630A2 (en) * | 2004-10-19 | 2006-05-04 | Arkema France | Metal surfaces coated with fluoropolymers |
| FR2902794A1 (en) * | 2006-11-10 | 2007-12-28 | Solvay | New fluorinated polymers grafted with a compound containing an organic group having an ethylenically unsaturated carbon-carbon bond and at least two alcohol groups, useful e.g. in pipes, tubes, transport/storage containers of hydrocarbons |
| US8211977B2 (en) | 2006-06-26 | 2012-07-03 | Solvay (Societe Anonyme) | Polymeric compositions with adhesive properties |
| US8372655B2 (en) | 2001-01-09 | 2013-02-12 | Protosera Inc. | Plate for mass spectrometry, process for preparing the same and use thereof |
| US9512255B2 (en) | 2010-12-28 | 2016-12-06 | Kureha Corporation | Vinylidene fluoride copolymers and uses of the copolymers |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003173781A (en) * | 2001-09-28 | 2003-06-20 | Mitsubishi Materials Corp | Paint for adhesive layer as well as electrode for secondary battery and secondary battery using them |
| JP2004220911A (en) * | 2003-01-15 | 2004-08-05 | Mitsubishi Materials Corp | Negative electrode material for lithium polymer battery, negative electrode using the same, lithium ion battery and lithium polymer battery using negative electrode |
| EP1505117A1 (en) * | 2003-08-01 | 2005-02-09 | Arkema | PVDF-based PTC paints and their applications for self-regulated heating systems |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1371843A (en) * | 1963-06-25 | 1964-09-11 | Centre Nat Rech Scient | Improvements to semi-permeable membranes |
| JPS5442931B2 (en) * | 1971-09-16 | 1979-12-17 | ||
| DE2559260C3 (en) * | 1975-12-31 | 1982-04-01 | Dynamit Nobel Ag, 5210 Troisdorf | Process for modifying polyvinylidene fluoride |
-
1980
- 1980-03-21 FR FR8006318A patent/FR2478649B1/en not_active Expired
-
1981
- 1981-02-02 IT IT19461/81A patent/IT1135264B/en active
- 1981-02-18 JP JP2164381A patent/JPS56133309A/en active Granted
- 1981-03-11 BE BE0/204082A patent/BE887892A/en not_active IP Right Cessation
- 1981-03-18 DE DE3110384A patent/DE3110384C2/en not_active Expired
- 1981-03-20 DK DK126481A patent/DK156441C/en not_active IP Right Cessation
- 1981-03-20 LU LU83242A patent/LU83242A1/en unknown
- 1981-03-20 CH CH1911/81A patent/CH647536A5/en not_active IP Right Cessation
- 1981-03-20 GB GB8108888A patent/GB2072203B/en not_active Expired
- 1981-03-20 NL NL8101388A patent/NL190930C/en not_active IP Right Cessation
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU608173B2 (en) * | 1988-08-22 | 1991-03-21 | Commonwealth Scientific And Industrial Research Organisation | Acid treated polyacrylic acid grafted fluorocarbon polymer surface for cell attachment |
| WO1990002145A1 (en) * | 1988-08-22 | 1990-03-08 | Commonwealth Scientific And Industrial Research Organisation | Acid treated polyacrylic acid grafted fluorocarbon polymer surface for cell attachment |
| GB2309701A (en) * | 1996-01-31 | 1997-08-06 | Aea Technology Plc | Organic electrolyte composition |
| EP0793286A1 (en) * | 1996-01-31 | 1997-09-03 | AEA Technology plc | Grafted polyvinylidene fluoride as a solid polymer electrolyte for eletrochemical cells, and electrochemical cell incorporating same |
| GB2309701B (en) * | 1996-01-31 | 1999-06-16 | Aea Technology Plc | Organic electrolyte composition |
| US6037080A (en) * | 1996-01-31 | 2000-03-14 | Aea Technology Plc | Organic electrolyte composition |
| WO1997032347A1 (en) * | 1996-02-27 | 1997-09-04 | Elf Atochem S.A. | Binders for electrodes and their production method |
| US6228533B1 (en) | 1996-02-27 | 2001-05-08 | Atofina | Electrodes with improved adhesion between activator and collector and methods of making the same |
| US8372655B2 (en) | 2001-01-09 | 2013-02-12 | Protosera Inc. | Plate for mass spectrometry, process for preparing the same and use thereof |
| WO2006042764A2 (en) * | 2004-10-19 | 2006-04-27 | Arkema France | Coating compositions for inorganic substrates |
| WO2006045630A3 (en) * | 2004-10-19 | 2006-07-13 | Arkema | Metal surfaces coated with fluoropolymers |
| WO2006042764A3 (en) * | 2004-10-19 | 2006-07-13 | Arkema | Coating compositions for inorganic substrates |
| CN101044216B (en) * | 2004-10-19 | 2011-02-09 | 阿克马法国公司 | Coating compositions for inorganic substrates |
| US8182912B2 (en) * | 2004-10-19 | 2012-05-22 | Arkema France | Coating compositions for inorganic substrates |
| WO2006045630A2 (en) * | 2004-10-19 | 2006-05-04 | Arkema France | Metal surfaces coated with fluoropolymers |
| US8211977B2 (en) | 2006-06-26 | 2012-07-03 | Solvay (Societe Anonyme) | Polymeric compositions with adhesive properties |
| FR2902794A1 (en) * | 2006-11-10 | 2007-12-28 | Solvay | New fluorinated polymers grafted with a compound containing an organic group having an ethylenically unsaturated carbon-carbon bond and at least two alcohol groups, useful e.g. in pipes, tubes, transport/storage containers of hydrocarbons |
| US9512255B2 (en) | 2010-12-28 | 2016-12-06 | Kureha Corporation | Vinylidene fluoride copolymers and uses of the copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3110384A1 (en) | 1982-02-25 |
| CH647536A5 (en) | 1985-01-31 |
| LU83242A1 (en) | 1983-02-22 |
| IT8119461A0 (en) | 1981-02-02 |
| GB2072203B (en) | 1984-07-25 |
| FR2478649A1 (en) | 1981-09-25 |
| FR2478649B1 (en) | 1985-06-21 |
| DE3110384C2 (en) | 1984-03-22 |
| NL190930B (en) | 1994-06-01 |
| JPH0138124B2 (en) | 1989-08-11 |
| BE887892A (en) | 1981-09-11 |
| NL8101388A (en) | 1981-10-16 |
| DK156441C (en) | 1990-01-02 |
| DK126481A (en) | 1981-09-22 |
| JPS56133309A (en) | 1981-10-19 |
| DK156441B (en) | 1989-08-21 |
| IT1135264B (en) | 1986-08-20 |
| NL190930C (en) | 1994-11-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990320 |