DK156441B - COATING COPOLYMERS FROM POLYVINYLIDEEN FLUORIDE AND ITS USE FOR METAL COATING - Google Patents
COATING COPOLYMERS FROM POLYVINYLIDEEN FLUORIDE AND ITS USE FOR METAL COATING Download PDFInfo
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- DK156441B DK156441B DK126481AA DK126481A DK156441B DK 156441 B DK156441 B DK 156441B DK 126481A A DK126481A A DK 126481AA DK 126481 A DK126481 A DK 126481A DK 156441 B DK156441 B DK 156441B
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- coating
- copolymers
- water
- pvdf
- polymer
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- 238000000576 coating method Methods 0.000 title claims description 20
- 229920001577 copolymer Polymers 0.000 title claims description 6
- 239000011248 coating agent Substances 0.000 title description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title 1
- 239000002033 PVDF binder Substances 0.000 claims description 33
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 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 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 238000001914 filtration 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
- 238000004448 titration Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition 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
- 238000001035 drying Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 235000013372 meat Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZTPQLYJGPLYBPS-UHFFFAOYSA-N phosphanylidynechromium Chemical compound [Cr]#P ZTPQLYJGPLYBPS-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
Description
DK 156441 BDK 156441 B
Deri foreliggende opfindelse angâr podningscopolymere ud fra polyvinylidenfluorid (PVDF) og ethylenisk umættede monomère samt disses anvendelse til metalovertræk.The present invention relates to graft copolymers based on polyvinylidene fluoride (PVDF) and ethylenically unsaturated monomers as well as their use in metal coatings.
5 PVDF er velkendt for ’sin modstandsdygtighed over for ke-miske virkemidler og over for ultraviolet strâling sâvel soin over for slibende pâvirkning. Aile disse gode egenskaber gor PVDF til et ideelt materiale til anvendelse udendors og i særdeleshed til beskyttelse af metaller.PVDF is well known for its resistance to chemical agents and to ultraviolet radiation as well as abrasive action. All these good properties make PVDF an ideal material for outdoor use and in particular for the protection of metals.
10 Denne sidste anvendelse bar dog hidtil ikke været fuldt tilfredsstillende pâ grund af manglen pâ PVDF*s klæbe-evne direkte over for metaller. De eneste kendte overtræk baseret pâ PVDF nodvendiggor stedse anbringelsen af et mellemliggende, klæbende lag mellem metallet og PVDF.10 However, this last application has not hitherto been fully satisfactory due to the lack of the adhesive ability of PVDF * directly to metals. The only known coatings based on PVDF necessitate the application of an intermediate adhesive layer between the metal and PVDF.
15 Det er fra DE-OS 25 59260 kendt, at vedhæftningen af PVDF pâ metaller lader sig forbedre, nâr det er modificeret ved podning med umættede monomère. I USA patentskrift nr, 3 839 172 omtales kun modifikation af polytetrafluorethylen med (meth)acrylsyre.15 It is known from DE-OS 25 59260 that the adhesion of PVDF to metals can be improved when modified by grafting with unsaturated monomers. U.S. Patent No. 3,839,172 discloses only modification of polytetrafluoroethylene with (meth) acrylic acid.
20 Man bar nu fastslâet, at det prodükt, som man opnâr ved indforing af podningsmateriale bestâende "af polyacryl- · syre eller polymethacrylsyre pâ et PVDF-skelet, ikke al» ene bevarer PVDF1 s egenskaber, men at materialet yder*» ligere besidder den egenskab, at det klæber direkte pâ 25 metaller uden et mellemliggende klæbelag. En sâdan podet polymer opnâs ved podningspolymerisation af acrylsyre eller af methacrylsyre pâ PVDF’s macromolekylære kæde. Podningen af disse polyacryl-kæder foregâr sædvanligvis pâ et skelet af homopolymer PVDF. Man kan dog undertiden 30 i tilknytning til den homopolymere hâve en copolymer in-deholdende mindst 90% vinylidenfluoridgrupper, idet sâ-danne copolymere stadig har de for homopolymere PVDF karakteristiske egenskaber.It has now been established that the product obtained by introducing grafting material consisting of polyacrylic acid or polymethacrylic acid on a PVDF skeleton does not all retain the properties of PVDF1, but that the material provides * A grafted polymer is obtained by grafting polymerization of acrylic acid or of methacrylic acid onto the macromolecular chain of PVDF, but the grafting of these polyacrylic chains usually takes place on a skeleton of homopolymer PVD. 30 in association with the homopolymer have a copolymer containing at least 90% vinylidene fluoride groups, such copolymers still having the characteristics of homopolymeric PVDF.
Ansogningen angâr sâledes podningscopolymere af den i krav l's indledning nævnte art, og disse podningscopoly-The application thus concerns graft copolymers of the kind referred to in the preamble of claim 1, and these graft copolymers.
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2 mere er ejendommelige ved det i krav l's kendetegnen-de del anf0rte.2 more are peculiar to the characterizing part of claim 1.
Podningspolymerisationen er i sig selv velkendt. Den bestâr i, at man bringer PVDF, som i sit skelet besidder 5 aktive grupper, i kontakt med den acrylmonomere til pod- ning ved en temperatur pâ mellem 50 og 80°C og i 4 - 12 timer. Omsætningen foregâr i nærvær af vand inde-holdende en vandoploselig inhibitor, som f.eks.The graft polymerization is well known in itself. It consists in contacting the PVDF, which has in its skeleton 5 active groups, with the acrylic monomer for grafting at a temperature between 50 and 80 ° C and for 4 - 12 hours. The reaction takes place in the presence of water containing a water-soluble inhibitor such as e.g.
CuSO^ eller FeSO^, for i storst mulig udstraek-10 ning at undgà dannelsen af acryl-homopolymere, som for-oger viskositeten i podningspolymerisations-mêdiet, og som bor frasepareres og bortkastes. Podningspolymerisationen kan ligeledes foregâ i nærvær af et oplosningsmid-del for FVDF. For at opnâ en podet polymer, der har en 15 god klæbeevne over for metaller, og som bevarer PVDF* s egenskaber, fæstnes mindst 2 vægt-% a£ den samle-de vægt podet polymer af polyacryl-podnings-inaterialet -til PVDF- skëlettet. Dersom man anvender pod-nings-reaktionsbetingelser, som forer til en hoj grad af 20 indfort methacrylsyre, er det muligt at blande dette po-dede produkt med en ikke-behandlet polymer til dannelse af oplosringer, som forer.til fast klæbende overtræk.CuSO4 or FeSO4, to the greatest extent possible to avoid the formation of acrylic homopolymers which increase the viscosity of the graft polymerization medium and which should be separated and discarded. The graft polymerization may also be carried out in the presence of a solvent for the FVDF. In order to obtain a grafted polymer having a good adhesive to metals and retaining the properties of PVDF *, at least 2% by weight of the total weight of grafted polymer of the polyacrylic grafting material to PVDF is attached. skeleton. If grafting reaction conditions leading to a high degree of methacrylic acid introduced are used, it is possible to mix this grafted product with an untreated polymer to form solutions which result in solid adhesive coatings.
Hoje indhold af podningsmateriale, særligt sâdanne, som overskrider 25 vægt-% polyacryl-podningsmateriale pâ 25 PVDF-skelettet, og som man opnâr med kraftigt bestrâlede produkter, er ikke særligt intéressante, efter som PVDF i stor udstrækning er nedbrudt gennem en for kraftig eks-ponering over for gamma- strâling.High levels of grafting material, especially those exceeding 25% by weight of polyacrylic grafting material on the 25 PVDF skeleton, and obtained with highly irradiated products, are not particularly interesting, since PVDF is widely decomposed by excessive vaporization. exposure to gamma radiation.
Til dannelse af aktive grupper pâ det anvendte skelet 30 bestrâles PVDF forud for podningspolymeri- sation. Bestrâling af polyvinylidenfluorid er velkendt? den er i^ær beskrevet i USA patentskrift nr. 4 137 137· Polyvinylidenfluorid underkastes i luft iondannende bestrâlinger. Disse iondannende bestrâlinger 35 stammer i praksis fra en kilde til gamma-strâling eller beta-strâling. Den strâlingsdosis, der er nodvendig for, at man kan udfore en effektiv podning, er en minimum be-To form active groups on the skeleton 30 used, PVDF is irradiated prior to graft polymerization. Irradiation of polyvinylidene fluoride is well known? it is described in U.S. Patent No. 4,137,137 · Polyvinylidene fluoride is subjected to air ionizing radiation. These ion-forming radiations 35 are in practice derived from a source of gamma radiation or beta radiation. The radiation dose required for effective grafting is a minimum requirement.
3 DK 156441 B3 DK 156441 B
strâling af polyvinylidenfluorid med mindst 3 x 10^ rad. Polyvinylidenfluoridet kan bestrâles i tilstand som uren-set polder eller som allerede mere eller mindre omdan-net polymer. For at opnâ den hojeste grad af tilgængelig-5 hcd for de aktive grupper bestrâler man sædvanligvid polyvinylidenfluoridet i form af et pulver, hvis partikelstor-relse kan variere fra ca. 0,2 til 100 yum, eller ogsâ i form af trâde pâ mindst 200 pm. Polyvinylidenfluoridet kan umiddelbart efter bestrâlingen bringes i kontakt med 10 den monomère med henblik pâ podningspolymerisationen, eller den kan opbevares, sædvanligvis ved en temperatur mindre end 10°C, indtil podningsbehandlingen.radiation of polyvinylidene fluoride of at least 3 x 10 5 rad. The polyvinylidene fluoride can be irradiated in the state as impure poles or as already more or less converted polymer. In order to obtain the highest degree of accessible-5 hcd for the active groups, the polyvinylidene fluoride is usually irradiated in the form of a powder, the particle size of which can vary from approx. 0.2 to 100 µm, or in the form of threads at least 200 µm. The polyvinylidene fluoride can be contacted immediately after irradiation with the monomer for the graft polymerization, or it can be stored, usually at a temperature less than 10 ° C, until the grafting treatment.
Ansogningen angâr som nævnt ogsâ anvendelsen af de podnings-copolymere til métalovertræk.As mentioned, the application also concerns the use of the graft copolymers for metal coatings.
15 Beskyttelsen af metaller ved bjælp af podet polymer fore-gâr pâ klassisk mâde, og sædvanligvis ved overtrækning af metalgenstande med termoplastiske materialer. Overtræk-ningen kan opnâ s ved torring i varmen, idet en temperatur pâ 200 °C er egnef, af en oplosning af pottet”"FVDF i et oplos-20 ningsmiddel, som f.eks. dimethylformamid, eller af en plastisol af det samme podede PVDF i latente oplosnings» midler, sâsom dimethylphthalat, diisobutylketon, iso-phoron, cyclohexanon eller blandinger deraf. Overtrækktîne kan ligeledes opnâs ved pâsprojtning af et pulver af podet 25 PVDF pâ metaloverfladen, der forinden er opvarmet til ca, 280 - 380°C; flere pâ hinanden folgende pâsprajtninger, som afveksler med behandling i ovn, kan foretages sâledes, at man kan regulere overtrækkets tykkelse. De opnâede overtræk er i særdeleshed meget vel klæbende 'pâ " stâl, pâ 30 galvaniseret stâl eller pâ aluminium. Pâ dette sidstnævn- te métal kan beklædningeme tâle et ophold pâ 70 timer i vand ved 120°C uden konstaterbar nedbrydning.15 The protection of metals by the use of grafted polymer takes place in the classical way, and usually by coating metal objects with thermoplastic materials. The coating can be obtained by drying in the heat, with a temperature of 200 ° C, of a solution of the pot "FVDF in a solvent, such as dimethylformamide, or of a plastisol of the same grafted PVDF in latent solvents such as dimethyl phthalate, diisobutyl ketone, iso-phorone, cyclohexanone or mixtures thereof. several successive sprays alternating with furnace treatment can be made to adjust the thickness of the coating. The coatings obtained are particularly well adhered to "steel", 30 galvanized steel or aluminum. In this latter case, the clothing can withstand a stay of 70 hours in water at 120 ° C without any detectable decomposition.
For pâforing af overtrækket underkastes de pâgældende pla-der fortrinsvis overfladebehandlinger, der er passende for 35 det pâgældende métal, og som i almindelighed gerniemfores for pâforingen af et hvilket som helst overtræk eller ma-For application of the coating, the sheets in question are preferably subjected to surface treatments suitable for the particular metal and which are generally laminated to the application of any coating or material.
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4 ling, sàsom affedtning, sandblæsning, kombineret behandling med phosphorforbindelser og chromforbindelser etc.4 ling, such as degreasing, sandblasting, combined treatment with phosphorus compounds and chromium compounds etc.
De felgende eksempler belyser opfindelsen.The following examples illustrate the invention.
EKSEMPEL 1 2 5 I en beholder pâ 500 cm , der er under omrering, og som be-finder sig under nitrogenatmosfære, anbringer man 50 g poly-vinylidenfluorid i pulverform opnâet ud fra en latex og be-strâlet med 0,8 Mrad, 93 g vand indeholdende 7 g methacryl-syre samt 0,050 g oplest CuSO^, 5H20. Man opvarmer ved 60°C 10 i 6 timer. Derpâ frasepareres det podede faste materiale ved filtrering, det terres og vaskes med vand pâ filteret, hvorpâ man terrer reaktionsproduktet i en ovn ved 100°C.EXAMPLE 1 2 5 In a 500 cm container under stirring, which is under a nitrogen atmosphere, 50 g of powdered polyvinylidene fluoride obtained from a latex is irradiated with 0.8 Mrad, 93 g of water containing 7 g of methacrylic acid and 0.050 g of dissolved CuSO4, 5H20. It is heated at 60 ° C for 6 hours. The inoculated solid is then separated by filtration, dried and washed with water on the filter, whereupon the reaction product is dried in an oven at 100 ° C.
Der opsamles 54 g ter polymer indeholdende 9,8% methacryl-syre. Syreindholdet bestemmes ved titrering med en oples-15 ning af kaliumhydroxid i methanol, den podede polymer op-leses i dimethylformamid, idet oplesningen tilsættes 25% vand fer titrering. Neutralisationspunktet fastlægges med pH-meter.54 g of polymer are collected containing 9.8% methacrylic acid. The acid content is determined by titration with a solution of potassium hydroxide in methanol, the grafted polymer is dissolved in dimethylformamide, the solution being added with 25% water after titration. The neutralization point is determined by pH meter.
EKSEMPEL 2 20 i samme reaktionsbeholder som i eksempel 1 anbringer man 50 g polyvinylidenfluorid i pulverform opnâet ud fra en latex og bestrâlet med 0,5 Mrad, 100 g vand indeholdende 5 g methacrylsyre og 0,03 g oplest CuSO^, 5H20. Der op-varmes ved 85°C i 6 timer.EXAMPLE 2 In the same reaction vessel as in Example 1, 50 g of powdered polyvinylidene fluoride obtained from a latex and irradiated with 0.5 Mrad, 100 g of water containing 5 g of methacrylic acid and 0.03 g of dissolved CuSO4, 5H20 are applied. It is heated at 85 ° C for 6 hours.
25 Man fraseparerer det podede faste stof ved filtrering, det vaskes og terres, idet man dispergerer produktet igen i vand og filtrerer det pâny. Det terres derpâ i ovn ved 120°C.The inoculated solid is separated by filtration, washed and terreshed, again dispersed in water and filtered. Then place it in the oven at 120 ° C.
Man opsamler 53,2 g polymer indeholdende 7,45% methacryl-30 syre. I vaskevandet bestemmes restindholdet af methacryl-53.2 g of polymer containing 7.45% methacrylic acid are collected. In the wash water, the residual content of the methacrylic acid is determined
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5 syre ved titrering, man finder 0,74 g syre og ved bestem-melse af dobbel tbindingeme 0,72 g methacrylsyre.5 acid by titration, 0.74 g of acid is found and in the determination of the double bonds 0.72 g of methacrylic acid is found.
EKSEMPEL 5 ocr sainmenlianincrsforsoqEXAMPLE 5 and Sainmenlianincursoq
Der fremstilles en 20 vægt%-opl0sning i dimethylformamid 5 :af hver af de .1 eksemplerne 1 og 2. .fremstillede po- dede polymère, sâvel som det ikke-bestrâlede oprindelige polyvinylidenfluorid. Man .fremstiller ligeledes en fjerde oplosning ved sammenblanding 4 lige store vægtmængder af en del ikke-bestrâlet oplosning af den oprindelige poly-10 mer samt af den i eksempel 22 .fremstillede polder. Plader af jern og af aluminium, der er affedtede, dekaperede med en phosphorchrom-blanding, ;og som er skyllet og torret, beklædes med disse fire oplosninger ved neddypning, hvor-’pâ de terres i ovn i et kvarter *ved 210°C. Samtlige over-15 træk klæber fast med undtagelse -af dë, som kun indeholder polyvinylidenfluorid, der lesnes fra underlaget ved simpel gnidn'ing med en negl.A 20% by weight solution in dimethylformamide 5 is prepared from each of the Examples 1 and 2. prepared grafted polymers, as well as the unirradiated original polyvinylidene fluoride. A fourth solution is also prepared by mixing 4 equal amounts of weight of some non-irradiated solution of the original polymer and of the poles prepared in Example 22. Sheets of iron and aluminum degreased, decapitated with a phosphorus chromium mixture, and rinsed and dried, are covered with these four solutions by immersion, whereupon they are placed in an oven in a neighborhood * at 210 ° C. . All overlays adhere to the exception except for those containing only polyvinylidene fluoride which is read from the substrate by simple rubbing with a nail.
De seks andre plader anbringes i en autoklav, der er halv-fyldt med vand, og opvarmes 72 timer ved 120°C. Efter den-20 ne behandling er det umuligt at starte adskillelsen i lim- ningen af overtrækket, selv om man skraber med en knivs-blad.The other six plates are placed in an autoclave half-filled with water and heated for 72 hours at 120 ° C. After this treatment, it is impossible to start the separation in the sizing of the coating, even if you scrape with a knife blade.
EKSEMPEL 4 og sammenligningsforsog I en reaktionsbeholder pâ 2 liter, der er under omrering 25 og under nitrogenatmosfære, anbringer man 500 g polyvinyli denf luorid, der er opnâet ved suspensions-polymeri sation· det foreligger i form af et pulver af storrelsen 40 - 100 yum og med tilsyneladende rumvægt pâ ca. 0,7. Det bestrâ-les med 1 Mrad. Derpâ tilsættes ligeledes 930 g vand inde-30 holdende 0,03 g CuSO^, 5H20 og 70 g destilleret methacryl syre. Der opvarmes ved 60°C i 6 timer,EXAMPLE 4 AND COMPARATIVE TRIAL In a 2 liter reaction vessel under stirring 25 and under nitrogen atmosphere, 500 g of polyvinylene difluoride obtained by suspension polymerization is applied in the form of a powder of size 40 - 100 µm. and with apparent space weight of approx. 0.7. It is irradiated with 1 Mrad. 930 g of water containing 0.03 g of CuSO4, 5H2O and 70 g of distilled methacrylic acid are also added. Heat at 60 ° C for 6 hours,
Man fraseparerer det podede faste stof ved filtrering, ter- 6The seeded solid is separated by filtration, ter 6
DK 156441 BDK 156441 B
i ovn ved 120 °C. Man opsamler en podet polymer, hvis meth-acrylsyreindhold er 12%.in oven at 120 ° C. A grafted polymer is collected whose methacrylic acid content is 12%.
Jemplader, der er affedtet og dekaperet soin ovenfor be-skrevet, opvarmes i ovn til 300 °C og ovërtrækkes ved over-5 pudring med et ikke-bestrâlet oprindeligt polyvinyliden-fluorid-pulver samt med polymerpulveret, der er podet med 12% methacrylsyre. Man gennemferer flere behandlinger med overpudring og med ophold i en ovn, indtil man opnâr en overtrækstykkelsë pâ ca. 200 yum. Der afsluttes med ét ' 10 ophold i ovn pâ 15 minutter og en neddypning i koldt vand af det stykke, der udtages af ovnen. Efter at være blevet ridset med en kniv og pâ denne mâde udsat for start af lesning, l0ser det ikke-bestrâlede oprindelige overtræk af FVDF sig ganske let, hvorimod overtrækket af podet 15 polymer klæber fuldstændigt, selv efter et ophold pâ 42 timer i vand ved 100°C.Boilers degreased and decapitated as described above are heated in the oven to 300 ° C and coated by powdering with an unirradiated original polyvinylidene fluoride powder as well as with the polymer powder grafted with 12% methacrylic acid. Several treatments are carried out with over-powdering and with staying in an oven until a coating thickness of approx. 200 yum. Finish with one '10 stays in the oven in 15 minutes and a soak in cold water of the piece taken out of the oven. After being scratched with a knife and in this way subjected to reading, the non-irradiated original coating of FVDF dissolves quite easily, whereas the coating of grafted 15 polymer adheres completely, even after a 42 hour soak in water at 100 ° C.
EKSEMPEL 5 I den i eksempel 1 anvendte reaktionsbeholder anbringes 100 g FVDF, der er opnâet ud fra en latex og bestrâlet 20 med 1 Mrad, 200 g vand indeholdendë 10 g acrylsyre og 0,05 g oplast CuSO^, 5H20. Der opvarmes ved 83°C i 6 timer.EXAMPLE 5 In the reaction vessel used in Example 1, place 100 g of FVDF obtained from a latex and irradiated 20 with 1 Mrad, 200 g of water containing 10 g of acrylic acid and 0.05 g of dissolved CuSO 4, 5H 2 O. Heat at 83 ° C for 6 hours.
Man fraseparerer den podede polymer ved filtrering, der t0rres og vaskes med vand pâ filteret, hvorpâ man terrer 25 reaktionsproduktet i ovn ved 100 °C.The seeded polymer is separated by filtration, dried and washed with water on the filter, whereupon the reaction product is dried in the oven at 100 ° C.
Der opsamles 101,5 g ter polymer indeholdende 4,9% acrylsyre bestemt ved titrering.101.5 g of polymer are collected containing 4.9% acrylic acid as determined by titration.
Som beskrevet i eksempel 3 fremstilles en 20%ig oplesning i dimethylformamid af den podede polymer, man overtrækker 30 en aluminiumplade og en stâlplade dermed, hvorpâ man var-As described in Example 3, a 20% solution in dimethylformamide is prepared from the grafted polymer, coating an aluminum plate and a steel plate therewith,
DK 156441 BDK 156441 B
•7 mebehandler 15 minutter i en ovn ved 210°C. Man iagttager for dette overtræk af polymer podet med acrylsyre den sam-me gode modstandsdygtighed over for kogende vand som for de med methacrylsyre podede polymère, der blev anvendt i 5 eksempel 3.• 7 meats for 15 minutes in an oven at 210 ° C. For this coating of polymer grafted with acrylic acid, the same resistance to boiling water is observed as for the polymers grafted with methacrylic acid used in Example 3.
EKSEMPEL 6 I en beholder pâ 500 cm^, ,der er under omroring og under nitrogenatmosfære, anbringer man 50 g pulverformig poly-vinylidenfluorid, der er opnâet ud fra en latex og be-10 .'strâlet med 3 Mrad, 75 g vand indeholdende 25 g methacrylsyre og 0,025 g oplost CuSO^, .5H20. Der opvarmes ved 60°C J. 6 timer. Man fraseparerer '-ved centrifugering det podede .faste stof, og det .disper-geres igen i vand og centrifu-geres pâny, hvorpâ man -terrer reaktionsproduktet i ovn 15 ved '100 °C.EXAMPLE 6 In a 500 cm 2 container stirred and under a nitrogen atmosphere, 50 g of powdered polyvinylidene fluoride obtained from a latex and 10 irradiated with 3 Mrad, 75 g of water containing 25 g of methacrylic acid and 0.025 g of dissolved CuSO It is heated at 60 ° C for 6 hours. By centrifugation, the grafted solid is separated by centrifugation and dispersed again in water and centrifuged to dry the reaction product in oven 15 at '100 ° C.
Man opsamler 62 g tor polymer indeholdende 24% methacrylsyre .62 g of dry polymer containing 24% methacrylic acid are collected.
Man anbringer 1 g af dette reaktionsprodukt sammen med 5 g ikke-bestrâlet, rent PVDF i oplosning i 30 g dimeth-20 ylformamid. Affedtede aluminiumplader overtrækkes med op- losningen ved neddypning, hvorpâ de torres et kvarter ved 210°C. Man iagttager den samme holdbarhed over for kogende vand som ved de andre podede polyvinylidenfluorid-overtræk, der er anvendt i eksempleme 3 og 5.One gram of this reaction product is applied together with five grams of unirradiated pure PVDF in solution in 30 grams of dimethylformamide. Degreased aluminum sheets are coated with the solution by immersion and dried for a quarter at 210 ° C. The same shelf life with boiling water is observed as with the other grafted polyvinylidene fluoride coatings used in Examples 3 and 5.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8006318 | 1980-03-21 | ||
| FR8006318A FR2478649B1 (en) | 1980-03-21 | 1980-03-21 | VINYLIDENE POLYFLUORIDE TREATED FOR ADHESION ON METALS, PROCESS FOR TREATMENT |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK126481A DK126481A (en) | 1981-09-22 |
| DK156441B true DK156441B (en) | 1989-08-21 |
| DK156441C DK156441C (en) | 1990-01-02 |
Family
ID=9239936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK126481A DK156441C (en) | 1980-03-21 | 1981-03-20 | COATING COPOLYMERS FROM POLYVINYLIDEEN FLUORIDE AND ITS USE FOR METAL COATING |
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) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5010009A (en) * | 1988-08-22 | 1991-04-23 | Commonwealth Scientific & Industrial Research Organisation & Telectronics Pty. Limited | Material for cell attachment and growth |
| 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 |
| DE69700138T2 (en) * | 1996-01-31 | 1999-09-02 | Aea Technology Plc | Polyvinylidene fluoride as a polymeric solid electrolyte for lithium-ion batteries |
| GB2309701B (en) * | 1996-01-31 | 1999-06-16 | Aea Technology Plc | Organic electrolyte composition |
| JPH09231977A (en) | 1996-02-27 | 1997-09-05 | Elf Atochem Japan Kk | Electrode and its manufacture |
| 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 |
| KR20050070034A (en) | 2002-10-04 | 2005-07-05 | 미쯔비시 웰 파마 가부시키가이샤 | Plate for mass spectrometry, process for preparing the same and use thereof |
| 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 |
| FR2876626B1 (en) * | 2004-10-19 | 2007-01-05 | Arkema Sa | USE OF A FLUORINATED POLYMER FOR PROTECTING THE SURFACE OF AN INORGANIC MATERIAL AGAINST CORROSION |
| WO2006045630A2 (en) * | 2004-10-19 | 2006-05-04 | Arkema France | Metal surfaces coated with fluoropolymers |
| FR2902794B1 (en) * | 2006-11-10 | 2010-06-18 | Solvay | FLUORINATED POLYMERS |
| JP5148604B2 (en) | 2006-06-26 | 2013-02-20 | ソルヴェイ（ソシエテ アノニム） | Polymer composition having adhesive properties |
| KR101520560B1 (en) | 2010-12-28 | 2015-05-14 | 가부시끼가이샤 구레하 | Vinylidene-fluoride-based copolymer and application of said copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839172A (en) * | 1963-06-25 | 1974-10-01 | Anvar | Radiation grafting of acrylic monomers onto perhalogenated olefin polymeric substrates |
| DE2559260A1 (en) * | 1975-12-31 | 1977-07-14 | Dynamit Nobel Ag | METHOD OF MODIFYING POLYVINYLIDEN FLUORIDE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442931B2 (en) * | 1971-09-16 | 1979-12-17 |
-
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 GB GB8108888A patent/GB2072203B/en not_active Expired
- 1981-03-20 DK DK126481A patent/DK156441C/en not_active IP Right Cessation
- 1981-03-20 CH CH1911/81A patent/CH647536A5/en not_active IP Right Cessation
- 1981-03-20 LU LU83242A patent/LU83242A1/en unknown
- 1981-03-20 NL NL8101388A patent/NL190930C/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839172A (en) * | 1963-06-25 | 1974-10-01 | Anvar | Radiation grafting of acrylic monomers onto perhalogenated olefin polymeric substrates |
| DE2559260A1 (en) * | 1975-12-31 | 1977-07-14 | Dynamit Nobel Ag | METHOD OF MODIFYING POLYVINYLIDEN FLUORIDE |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8119461A0 (en) | 1981-02-02 |
| NL8101388A (en) | 1981-10-16 |
| NL190930B (en) | 1994-06-01 |
| FR2478649B1 (en) | 1985-06-21 |
| BE887892A (en) | 1981-09-11 |
| FR2478649A1 (en) | 1981-09-25 |
| DE3110384A1 (en) | 1982-02-25 |
| DK156441C (en) | 1990-01-02 |
| IT1135264B (en) | 1986-08-20 |
| DE3110384C2 (en) | 1984-03-22 |
| GB2072203A (en) | 1981-09-30 |
| NL190930C (en) | 1994-11-01 |
| CH647536A5 (en) | 1985-01-31 |
| DK126481A (en) | 1981-09-22 |
| LU83242A1 (en) | 1983-02-22 |
| JPH0138124B2 (en) | 1989-08-11 |
| GB2072203B (en) | 1984-07-25 |
| JPS56133309A (en) | 1981-10-19 |
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| PBP | Patent lapsed |