CS256750B1 - Method of polymers' permanent treatment for increase of their electric conductivity - Google Patents
Method of polymers' permanent treatment for increase of their electric conductivity Download PDFInfo
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- CS256750B1 CS256750B1 CS86961A CS96186A CS256750B1 CS 256750 B1 CS256750 B1 CS 256750B1 CS 86961 A CS86961 A CS 86961A CS 96186 A CS96186 A CS 96186A CS 256750 B1 CS256750 B1 CS 256750B1
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- treated
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- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000011282 treatment Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 28
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000005749 Copper compound Substances 0.000 claims abstract description 5
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 5
- -1 sulphite ions Chemical class 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000004133 Sodium thiosulphate Substances 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000004763 sulfides Chemical class 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 239000004128 Copper(II) sulphate Substances 0.000 claims 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- LDQSYHTXJWPYKN-UHFFFAOYSA-N copper nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O LDQSYHTXJWPYKN-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000006184 cosolvent Substances 0.000 abstract 1
- 230000005611 electricity Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000001465 metallisation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KRPUGSACBHJZSR-UHFFFAOYSA-N [3-oxo-2-phenyl-3-(pyridin-2-ylmethylamino)propyl] acetate Chemical compound C=1C=CC=CC=1C(COC(=O)C)C(=O)NCC1=CC=CC=N1 KRPUGSACBHJZSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical class ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 101150101567 pat-2 gene Proteins 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Spósob permanentnej úpravy polymérov pre zvýšenie ich elektrickej vodivosti. Pod stata riešenia spočívá v tom, že na polymér- ny materiál, obsahujúci skupiny — Cl sa pri teplote 5 až 200 °C v kúpeli polárného roz púšťadla působí mednatou zlúčeninou v pří tomnosti redukčného činidla, a na takto pre- parovaný povrch sa působí organickou a/a lebo anorganickou zlúčeninou uvolňujúcou alebo obsahujúcou sulfitové ióny.cause permanent treatment polymers for increase their electricity conductivity. Come Stata solutions is in how that on the Polymer- ny material, containing groups - Cl the at at 5 until 200 ° C in bath polar extended a cosolvent acts copper compound in at presence reduction agents and on the thus for- pairing surface the acts organic a / a because inorganic compound which liberates or containing sulphite ions.
Description
Spósob permanentnej úpravy polymérov pre zvýšenie ich elektrickej vodivosti. Podstata riešenia spočívá v tom, že na polymérny materiál, obsahujúci skupiny —Cl sa pri teplote 5 až 200 °C v kúpeli polárného rozpúšťadla působí mednatou zlúčeninou v přítomnosti redukčného činidla, a na takto preparovaný povrch sa působí organickou a/alebo anorganickou zlúčeninou uvolňujúcou alebo obsahujúcou sulfitové ióny.A method of permanently treating polymers to increase their electrical conductivity. The solution consists in treating the polymeric material containing the —Cl groups at a temperature of 5 to 200 ° C in a polar solvent bath with a copper compound in the presence of a reducing agent, and treating the surface thus prepared with an organic and / or inorganic compound releasing or containing sulfite ions.
Vynález sa týká sposobu ipermanentneij úpravy polymérov. pre zvýšenie ich eltetóteackej vodivosti, pričom podmienky sú volené tak, že sa u výrobkov na .báze uvedených polymérov dosiahne požadovaná sOoistť .fftpravy proti fyzikálno-chemickému namáhaniu.The invention relates to a process for the permanent treatment of polymers. to increase their electrolytic conductivity, the conditions being selected such that the desired resistance to physicochemical stress treatment of the products based on said polymers is achieved.
Známe je, že čisté syntetické polyméry sú izolanty o špecifickom odpore rádovo 1012 až 1018 Ω . cm. Ako hranica elektrického odporu, pod ktorou sú materiály prakticky neelektrizovateiné, t. j. nevytvárajú statický náboj, sa uvádza hodnota menšia ako ΙΟ9 Ω .It is known that pure synthetic polymers are insulators having a specific resistance of the order of 10 12 to 10 18 Ω. cm. The value of less than ΙΟ 9 uvádza is given as the limit of electrical resistance below which the materials are practically non-electrisable, ie they do not generate static charge.
. cm — antistatické materiály.. cm - antistatic materials.
V súčasnosti poznáme niekolko spůsobov úpravy polymérnych materiálov, ktorými sa dosahuje zvýšenie elektrickej vodivosti, například metalizácia, resp. nanášanie na povrch ionizovaných a hygroskopických látok, plnenie kovovými alebo uhlíkovými časticami a pod.Nowadays we know several ways of treatment of polymeric materials, which achieve increase of electrical conductivity, for example metallization, resp. application to the surface of ionized and hygroscopic substances, filling with metal or carbon particles and the like.
Najdóležitejšie metódy nanášania kovových vrstiev na polyméry možeme rozdělit na fyzikálně, elektrochemické a chemické, pričom sa kov nanáša v plynnej fáze alebo v roztoku.The most important methods of applying metal layers to polymers can be divided into physical, electrochemical and chemical, where the metal is applied in the gas phase or in solution.
Chemická metalizácia polyméru v roztoku pozostáva z povrstvenia povrchu kovom pomocou rozpustného redukovatelného činidla. Hybnou silou autokatalytického procesu zabudovanie iónov kovu na povrchu polyméru je katalytické okysličenie redukovatelného ičinidla, ktoré a dostatečnou intenzitou prebieha na niektorých ko-voch s katalytickými vlastnosťami. Nanesenie týchto kovov na povrch polymérneho materiálu sa nazýva aktiváciou, ktorá může pozostávať z dvoch etáp, a to senzibilizácie a aktivácle. Senzibilizácia sa spravidla vykonává v roztokoch solí dvojmocného cínu. Aktiv ácia po seiizibilizácii sa robí v roztokoch solí a komploxných zlúčenín ušlechtilých kovov váčšiuou za použitia paládia alebo striebra.The chemical metallization of the polymer in solution consists of coating the surface with a metal using a soluble reducing agent. The driving force of the autocatalytic process of incorporating metal ions on the polymer surface is the catalytic oxygenation of the reducible reagent, which takes place with sufficient intensity on some metals with catalytic properties. The deposition of these metals on the surface of the polymeric material is called activation, which may consist of two stages, namely sensitization and activating. Sensitization is generally carried out in tin (II) salt solutions. Activation after seizibilization is made more difficult by using palladium or silver in solutions of salts and complex compounds of noble metals.
Podfa JAP PAT 5 337 912 sa kov vnesie do polymérneho povrchu tak, že polymérny klasický pokovovaný materiál sa rozmělní na částice, ktoré sa následné nanesú na základný polymérny materiál.According to JAP PAT 5 337 912, the metal is introduced into the polymer surface by grinding the polymeric classic metallized material into particles, which are subsequently applied to the base polymer material.
USA PAT 4 405 394 popisuje sposob povrchovej úpravy povrstvením termoplastického laminátového plošného polymérneho útvaru na epoxidovém substráte méďou alebo hliníkom.U.S. Pat. No. 4,405,394 describes a surface treatment method by coating a thermoplastic laminate sheet polymer structure on an epoxy substrate with copper or aluminum.
USA PAT 3 962 497 popisuje sposob zlepšenia elektrických vlastností polymérov redukcíou iónov šesfmocného chrómu na trojmocný účinkom roztoku síranu železnatého alebo soli bydroxylamínu v. kyslom prostředí.U.S. Pat. No. 3,962,497 describes a method for improving the electrical properties of polymers by reducing hexavalent chromium ions to trivalent by the ferrous sulfate solution or the dihydroxylamine salt of. acid environment.
ZSSR AO 425 985 popisuje metalizáciu polymérnych povrchov niklom, železom, zlatom, kobaltom, vanádom, mangánom, zinkom a kadmiom karbonylovou metodou pri teplote minimálně 300 °C. Sposobmi chemickej metalizácie vo vákuových komorách sa zaoberajú ZSSR AO 699 031, USA PAT číslo 3 355 318 a franc. PAT 2 348 941.USSR AO 425 985 describes the metallization of polymer surfaces by nickel, iron, gold, cobalt, vanadium, manganese, zinc and cadmium carbonyl at a temperature of at least 300 ° C. Methods of chemical metallization in vacuum chambers are dealt with in USSR AO 699 031, U.S. Pat. No. 3,355,318 and French Pat. PAT 2,348,941.
Ďalším spůsobom aískania metalopolymérnytíh povrchov polymérov je vytvorenie koloidných častíc kovu v hmotě polyméru (KorjukinA. V.·: Metalo,polymernyje pokrytja polymeMHz, Moskva, Izdat. Chimija 1983 j.Another method of scavenging the metallopolymer polymer surfaces is the formation of colloidal metal particles in the polymer mass (KorjukinA V. V.: Metallo, polymernyje krytja polymeMHz, Moscow, Izdat. Chimija 1983 j.
USA PAT 4 566 991 popisuje získanie dobrých antistatických vlastností 4,6 . 1O10 — 8,7.1011 Ω . cm, oproti neupravenému PA-6U.S. Pat. No. 4,566,991 discloses obtaining good antistatic properties 4.6. 1O 10 - 8.7.10 11 Ω. cm, untreated PA-6
1. ΙΟ15 Ω . cm, spósobom vytvorenia polymérneho kompozitu zmiešaním polyméru a kovověj soli v hmotě a následnou povrchovou úpravou uhličitanmi, sírnikmi alebo oxidmi vo vodnej alebo plynnej fáze.1. ΙΟ 15 Ω. cm, by forming a polymer composite by mixing the polymer and the metal salt in the mass followed by surface treatment with carbonates, sulfides or oxides in the aqueous or gas phase.
Franc. PAT 2 181 482 a USA PAT 3 910 533 popisujú proces fixácie kovových zlúčenín na textilně materiály zo syntetických polymérov působením plynného sirovodíka alebo vodných rožtokov sírnych zlúčenín, obsahujúcich reaktívny atom síry a následné pósobenie roztokov solí kovov.Franc. U.S. Pat. No. 2,181,482 and U.S. Pat. No. 3,910,533 disclose a process for fixing metal compounds to textile materials of synthetic polymers by treatment with hydrogen sulfide gas or aqueous solutions of sulfur compounds containing a reactive sulfur atom and the subsequent action of metal salt solutions.
Franc. PAT 2 264 482 a USA PAT 3 983 286 popisujú proces úpravy ako v predchádzajúcich dvoch patentových spisoch, kde okrem roztoku kovověj soli sa používá v upravárenskom kúpell ibobtnadlo vhodné pre upravovaný materiál.Franc. PAT 2,264,482 and U.S. Pat. No. 3,983,286 disclose a treatment process as in the previous two patents where, in addition to a metal salt solution, an ibobaltant suitable for the material being treated is used in the treatment bath.
USA PAT 4 374 893 popisuje antistatické textilně výrobky so stálými elektrovodivými vlastnosťami, ktoré sa dosahujú použitím vláken s povrchovou vrstvou obsahujúcou minimálně 3 % sírnikov médi, ktoré sa vytvárajú působením plynného sirovodíka na Textíliu za posobenia Tlaku ,a následným účinkom vodného roztoku síranu mědnatého a redukčného činidla. Ten istý princip úpravy popisuje aj GB PAT 2 078 545.U.S. Pat. No. 4,374,893 discloses antistatic textile products having permanent electro-conductive properties which are achieved by using fibers having a surface layer containing at least 3% of sulfides of the media formed by the action of a hydrogen sulfide on the pressure imparting fabric and the subsequent effect of an aqueous copper sulfate and reducing solution. agents. The same treatment principle is also described in GB PAT 2 078 545.
USA PAT 4 378 226 popisuje úpravu syntetických vláken sírnikmi médi,. pričom do upravovaného -polyméru sú různými formami kopolymerizácie zabudované nitrilové skupiny. Ďalšie úpravy polymérov za účelom zníženia ich elektrického odporu sú popisané v .početných patentových spisoch například USA PAT 4.362 779; 4 287 254; 4 336-028; 4 410-593; lEurop. .PAT 35 406, JAP PAT číslo 5Ι2.358Ό00; 58 018 445; 59Ό21 722, Franc. PAT 2 272 567.U.S. Pat. No. 4,378,226 describes the treatment of synthetic fibers with sulfide media. wherein nitrile groups are incorporated into the polymer to be treated by various forms of copolymerization. Other modifications of polymers to reduce their electrical resistance are described in numerous patents, for example, U.S. Pat. No. 4,362,779; 4,287,254; 4 336-028; 4 410-593; leurope. .PAT 35 406, JAP PAT No. 5Ι2.358Ό00; 58,018,445; 59-21 722, Franc. PAT 2,272,567.
Nevýhodou súčasného stavu u pokovovaných povrchov sú poměrně komplikované a nákladné metódy, diskutabilně přilnavost kovověj vrstvy hlavně v miestach exponovaných na dynamické namáhanie. Pri karbonylovej metóde sa vyžaduje teplota minimálně 300 °C, čo je u běžných polymérnych materiálov obsahujúcich skupiny —Cl přesahuje teplotu rozkladu. Přítomnost kovových alebo uhlíkových častíc v hmotě polyméru vačšinou ovplyvňuje důležité vlastnosti polyméru a vyžaduje vysokú koncentráciu vodivých častíc v hmotě pre dosiahnutie požadovaného efektu. Úpravy povrchov prídavkom ionizovaných a hygroskopických látok sú často citlivé a nestále pri vyššej teplote. Niektoré z uvedených postupov sú ohraničené na polymery obsahujúce — CN sku256750 piny, resp. nesu rizika z hladiska ochrany životného a pracovného prostredia.The disadvantage of the present state of metallized surfaces is the relatively complicated and costly methods, debatably the adhesion of the metal layer mainly in places exposed to dynamic stress. The carbonyl method requires a temperature of at least 300 ° C, which is above the decomposition temperature of conventional polymer materials containing the —Cl groups. The presence of metal or carbon particles in the polymer mass usually affects the important properties of the polymer and requires a high concentration of conductive particles in the mass to achieve the desired effect. Surface treatments by the addition of ionized and hygroscopic substances are often sensitive and volatile at higher temperatures. Some of the above procedures are limited to polymers containing - CN sku256750 pins, respectively. the environmental and working environment.
Uvedené a ďalšie nevýhody známého stavu rieši tento- vynález, pódia ktorého sposob permanentnej úpravy polymérov, pře zvýšenie ich elektrickej vodivosti sa robí tak, že na polymérny materiál, obsahujúci skupiny —Cl sa pri teplote 5 až 200 °C v kúpeli polárného rozpúšťadla, s výhodou vody, posobí meďnatou zlúčeninou v přítomnosti redukčného činidla, a na takto preparovaný povrch sa posobí organickou a/alebo anorganickou zlúčeninou uvolňujúcou alebo obsahujúcou sulfitové ióny.These and other disadvantages of the known state of the art are solved by the present invention, in which the method of permanently treating the polymers, in order to increase their electrical conductivity, is to produce a polymeric material containing the —Cl groups at a temperature of 5 to 200 ° C. preferably water, impregnates the copper compound in the presence of a reducing agent, and impregnates the surface thus prepared with an organic and / or inorganic compound releasing or containing sulfite ions.
Výhody postupu pódia vynálezu sú vo vysokej variabilitě stavu a formy upravovaného —Cl obsahujúceho polymeru — prášok, granulát, vlákno, vlákenná častica, folia, doska, priestorový výrobok atd'. Ďalšou výhodou postupu je skutočnosť, že viazanie elektricky aktívnej zlúčeniny na polymer zaisfuje vysokú stálost úpravy vcči mechanickému, chemickému a tepelnému namáhaniu výrobku.The advantages of the process according to the invention are in the high variability of the state and form of the treated Cl-containing polymer - powder, granulate, fiber, fiber particle, foil, board, spatial product, etc.. A further advantage of the process is that the binding of an electrically active compound on the polymer reinsurance f U is the high stability of the treatment VCCI mechanical, chemical and thermal stresses of the product.
Princip úpravy povrchu polymérnych materiálov obsahujúcich skupiny —Cl, spočívá v naviazaní dvoj-, ale přednostně jednomocnej médi koordinačně na uvedenú skupinu, ktorá ako ligand koordinačnej zlúčeniny podporuje redukciu Cu2+ na Cu+. Na koordinačně viazané ióny médi sa v dalšom procese úpravy viažu sulfidové ióny, čím vznikajú sírniky médi s pKs 35,2 (CuS) až 47,6 (CužSj.The principle of surface treatment of polymeric materials containing groups -Cl consists in attaching a bivalent but preferably monovalent medium to a coordinating group on said group, which as a ligand of the coordinating compound promotes the reduction of Cu 2+ to Cu + . Sulfide ions are bound to the coordinated-bound media ions in the next treatment process, resulting in sulfides of media with a pK of 35.2 (CuS) to 47.6 (CuS1).
Na přípravu kúpeia polárného rozpúšfadla je možné okrem destilovanej a demineralizovanej vody použit aj pramenitú vodu, pretože přísady solí neznižujú jeho účinok. Aj keď sa ako kúpel', s výhodou používá voda, bez straty na účinku móže túto funkciu plnit aj iné rozpúšťadlo, napr. zriedené roztoky kyselin, iónových alebo neiónových tenzidov, resp. zmes rozpúšťadiel.In addition to distilled and demineralized water, spring water can also be used to prepare the polar solvent, since the addition of salts does not reduce its effect. Although water is preferably used as a bath, another solvent, e.g. dilute solutions of acids, ionic or nonionic surfactants, respectively. mixture of solvents.
Redukčným a sulfidačným činidlom móže byť jediná zlúčenina, napr. tioacetamid, tiosíran sodný a pod., ale aj v tomto případe je výhodnější postup dvojstupňový. Aj pri viacstupňovom postupe je výhodné postupovat jednokúpeiovo s postupným přidáváním reagentov.The reducing and sulfidating agent may be a single compound, e.g. thioacetamide, sodium thiosulfate and the like, but even in this case, the two-step process is more preferred. Even in a multistage process, it is advantageous to proceed in a single bath with the stepwise addition of reagents.
Nasledujúce příklady ilustrujú vynález, ale žiadnym spósobom ho nelimitujú.The following examples illustrate the invention but do not limit it in any way.
Příklad 1Example 1
Do vodného kúpeia s teplotou 20 °C a pH rovnajúcom sa 4 obsahujúceho 0,05 molu. .I1 síranu mědnatého a 0,005 molu . Γ1 tiosíranu sodného sa vnesie polyvinylchloridový (PVC) prášok pri pomere kúpeia 1 : 15 a za stálého miešania zohreje na teplotu 70 °C. Pri tejto teplote sa přidá ďalšia časť tiosíranu sodného na celkovú koncentráciu 0,01 molu . 1_1 a teplota sa zvýši na 100 °C. Pri tejto teplote sa za stálého miešania v priebehu 60 minút prášok upraví. Upravený PVC prášok je olivovo-zelenej farby a je vhodný pre spracovanie běžnými technológiami. Elektrický odpor výrobku dosiahol hodnotu ΙΟ6 Ω.To a water bath at a temperature of 20 ° C and a pH of 4 containing 0.05 moles. 1 cupric sulphate and 0.005 mol. Γ 1 sodium thiosulphate is introduced with a polyvinyl chloride (PVC) powder at a 1:15 buying ratio and heated to 70 ° C with stirring. At this temperature an additional portion of sodium thiosulfate is added to a total concentration of 0.01 mol. 1 1 and the temperature raised to 100 ° C. At this temperature, the powder is treated with stirring for 60 minutes. The treated PVC powder is olive-green in color and is suitable for processing by conventional technologies. The electrical resistance of the product has reached ΙΟ 6 Ω.
Příklad 2Example 2
Do vodného kúpela s teplotou 20 °C obsabujúceho ditioničitan sodný o koncentrácii 0,06 molu . I“1 sa vnesie polyvinylchloridový (PVC) prášok pri pomere kúpeia 1:10 a za stálého miešania sa zohreje na teplotu 40 °C, pri ktorej sa upravuje 10 minút. Potom sa přidá síran mědnatý na koncentráciu 0,2 mólu. i1 a teplota sa zvýši na 100 °C. V tejto fáze sa PVC prášok upravuje po dobu 30 minút. Po tejto fáze následuje ochladenie na 50 °C a přidá sa tiosíran sodný na výslednú koncentráciu 0,13 molu . I-1. Teplota sa zvýši na 100 °C. Táto fáza úpravy trvá 30 minút. Upravený prášok je tmavohnědý a je vhodný pre spracovanie běžnými technológiami. Elektrický odpor hotového výrobku dosahuje ΙΟ5 Ω.To a 20 ° C water bath containing 0.06 mol of sodium dithionite. I '1 is loaded polyvinyl chloride (PVC) powder at a liquor ratio 1:10, and the stirred solution heated to 40 ° C where it is modified for 10 minutes. Copper sulphate is then added to a concentration of 0.2 mol. 1 and the temperature raised to 100 ° C. At this stage, the PVC powder is treated for 30 minutes. This phase is followed by cooling to 50 ° C and sodium thiosulfate is added to a final concentration of 0.13 mol. I -1 . The temperature was raised to 100 ° C. This adjustment phase takes 30 minutes. The treated powder is dark brown and is suitable for processing by conventional techniques. The electrical resistance of the finished product is ΙΟ 5 Ω.
Příklad 3Example 3
Postupuje sa ako v příklade 1, len s tým rozdielom, že namiesto tiosíranu sodného sa použije tioacetamid o koncentrácii 0,1 mólu.The procedure is as in Example 1, except that 0.1 mole thioacetamide is used instead of sodium thiosulfate.
. l-i.. l-i.
Příklad 4Example 4
Postupuje sa ako v příklade 1, len s tým rozdielom, že namiesto síranu mědnatého sa použije mědnatý komplex kyseliny nitrilotrioctovej o koncentrácii 0,1 mólu . I-1.The procedure is as in Example 1, except that copper nitrile triacetic acid complex of 0.1 mol concentration is used instead of copper sulfate. I -1 .
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS86961A CS256750B1 (en) | 1986-02-12 | 1986-02-12 | Method of polymers' permanent treatment for increase of their electric conductivity |
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| Application Number | Priority Date | Filing Date | Title |
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| CS86961A CS256750B1 (en) | 1986-02-12 | 1986-02-12 | Method of polymers' permanent treatment for increase of their electric conductivity |
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| Publication Number | Publication Date |
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| CS96186A1 CS96186A1 (en) | 1987-09-17 |
| CS256750B1 true CS256750B1 (en) | 1988-04-15 |
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| CS86961A CS256750B1 (en) | 1986-02-12 | 1986-02-12 | Method of polymers' permanent treatment for increase of their electric conductivity |
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1986
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| CS96186A1 (en) | 1987-09-17 |
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