CN108929453A - The preparation method of antistatic silicone rubber - Google Patents
The preparation method of antistatic silicone rubber Download PDFInfo
- Publication number
- CN108929453A CN108929453A CN201810686792.0A CN201810686792A CN108929453A CN 108929453 A CN108929453 A CN 108929453A CN 201810686792 A CN201810686792 A CN 201810686792A CN 108929453 A CN108929453 A CN 108929453A
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- surfactant
- coating
- silicon rubber
- antistatic
- 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.)
- Pending
Links
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 189
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000002216 antistatic agent Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 60
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 40
- 239000004094 surface-active agent Substances 0.000 claims description 31
- 238000004381 surface treatment Methods 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- JXYZHMPRERWTPM-UHFFFAOYSA-N hydron;morpholine;chloride Chemical compound Cl.C1COCCN1 JXYZHMPRERWTPM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 150000002462 imidazolines Chemical class 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229920000260 silastic Polymers 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 33
- 238000004140 cleaning Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000005507 spraying Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 16
- 230000001678 irradiating effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- TXTIIWDWHSZBRK-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CO.CC1=CC=C(N=C=O)C=C1N=C=O TXTIIWDWHSZBRK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- JRCDZZHCHHUWLU-UHFFFAOYSA-N [N+](=O)(O)[O-].C(CCCCCCCCCCCCCCC)N1CC=CC=C1 Chemical compound [N+](=O)(O)[O-].C(CCCCCCCCCCCCCCC)N1CC=CC=C1 JRCDZZHCHHUWLU-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- LOCPTSFJZDIICR-UHFFFAOYSA-N 1,3-bis(3-isocyanato-4-methylphenyl)-1,3-diazetidine-2,4-dione Chemical compound C1=C(N=C=O)C(C)=CC=C1N1C(=O)N(C=2C=C(C(C)=CC=2)N=C=O)C1=O LOCPTSFJZDIICR-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- KBCVENKEACAKMN-UHFFFAOYSA-N 2-[[2,3-bis(oxiran-2-ylmethoxy)-1-propoxypropoxy]methyl]oxirane Chemical compound C(C1CO1)OC(C(OCC1CO1)COCC1CO1)OCCC KBCVENKEACAKMN-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZFVMURAXVFXYSE-UHFFFAOYSA-M P(=O)([O-])(O)O.C(CCCCCCCCCCC)(=O)O.C(CCCCCCCCCCC)(=O)O.[Na+] Chemical compound P(=O)([O-])(O)O.C(CCCCCCCCCCC)(=O)O.C(CCCCCCCCCCC)(=O)O.[Na+] ZFVMURAXVFXYSE-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- BWCJYRAABYOMBE-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.CCCCCCCCCCCCCCCC[N+](C)(C)C BWCJYRAABYOMBE-UHFFFAOYSA-M 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPDJEKMSFIRVII-UHFFFAOYSA-N oxomethylidenehydrazine Chemical compound NN=C=O RPDJEKMSFIRVII-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to the preparation method of antistatic silicone rubber, the preparation method includes: to provide a silicon rubber, is surface-treated to the silicon rubber, makes the silastic surface with polar group；Polyfunctional compound is overlying on the surface of the silicon rubber with polar group and forms first coating, the polyfunctional compound is made to react to form chemical bond with the polar group；Antistatic agent and binder are overlying on the surface of the first coating and form second coating, the binder is made to react to form chemical bond with the polyfunctional compound, then it is cured after obtain antistatic silicone rubber.Preparation method of the present invention is first surface-treated silicon rubber, then forms the coating containing antistatic agent in silastic surface, plays the role of permanent anti-static.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a preparation method of antistatic silicone rubber.
Background
The polymer material is easy to be charged with static electricity, and if the static electricity is generated and is not removed in time, accumulation is easy to occur, so that dust absorption, electric shock and even explosion and other serious accidents are caused after sparks are generated. In the electronic communications industry, the accumulation of static electricity can damage integrated circuit semiconductor components, causing electronic devices, machinery, and the like to malfunction. Moreover, the presence of static electricity can cause interference to wireless communication equipment, generate noise, and affect signal transmission. Therefore, antistatic treatment of the polymer material is required.
At present, the antistatic treatment method of the high polymer material is mainly to add an antistatic agent in the preparation process of the high polymer material. Silicone rubber is a high molecular material with good performance, but, because the solubility parameter of the organic siloxane (-Si-O-) of the silicone rubber is far lower than that of other compounds and materials, and the surface tension of the silicone rubber is small, the silicone rubber has obvious incompatibility, namely is not easy to mix with other materials. When the antistatic agent is added into the silicone rubber, the silicone rubber and the antistatic agent are incompatible, so that the antistatic agent is easy to migrate, and the long-term service performance and the antistatic performance of the material are influenced. Therefore, it is difficult for the silicone rubber to achieve antistatic purpose by directly adding an antistatic agent.
Disclosure of Invention
Therefore, it is necessary to provide a preparation method of antistatic silicone rubber aiming at the problem of poor compatibility of silicone rubber and antistatic agent, wherein the preparation method comprises the steps of firstly carrying out surface treatment on silicone rubber, and then forming a coating containing the antistatic agent on the surface of the silicone rubber to play a permanent antistatic role.
A preparation method of antistatic silicone rubber comprises the following steps:
providing silicon rubber, and carrying out surface treatment on the silicon rubber to enable the surface of the silicon rubber to be provided with polar groups;
coating a multifunctional compound on the surface of the silicone rubber with the polar group to form a first coating, and reacting the multifunctional compound with the polar group to form a chemical bond;
and coating an antistatic agent and a binder on the surface of the first coating to form a second coating, reacting the binder with the polyfunctional compound to form a chemical bond, and curing to obtain the antistatic silicone rubber.
In one embodiment, the surface treatment method includes an ultraviolet light irradiation treatment method or a plasma surface treatment method; wherein,
the ultraviolet light irradiation treatment method is performed in an ozone atmosphere;
the plasma surface treatment method is performed in an oxygen atmosphere.
In one embodiment, the wavelength of the ultraviolet light in the ultraviolet light irradiation treatment method is 100nm to 300 nm; and/or
The temperature of the ultraviolet light irradiation treatment method is 20-200 ℃, and the time is 1-120 minutes.
In one embodiment, the plasma surface treatment is performed at a temperature of 20 ℃ to 200 ℃ for 1 minute to 120 minutes.
In one embodiment, the polar group is a hydroxyl group.
In one embodiment, after the first coating is formed, the temperature is maintained at 20 ℃ to 150 ℃ for 1 minute to 60 minutes.
In one embodiment, the multifunctional compound includes at least one of a silane coupling agent, a polyisocyanate, and a multifunctional epoxy compound.
In one embodiment, the silane coupling agent comprises at least one of 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane.
In one embodiment, the polyisocyanate includes a compound containing three or more isocyanate groups.
In one embodiment, the multifunctional epoxy compound includes a compound having three or more epoxy groups.
In one embodiment, the antistatic agent comprises at least one of a surfactant and a hydrophilic polymer.
In one embodiment, the surfactant comprises at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant; wherein,
the cationic surfactant comprises at least one of quaternary ammonium salt surfactant, morpholine hydrochloride surfactant or imidazoline salt surfactant;
the anionic surfactant comprises at least one of a sulfonate surfactant, a phosphate surfactant, or a carboxylate surfactant;
the nonionic surfactant includes at least one of a surfactant comprising a polyoxyethylene segment or a polyol.
In one embodiment, the hydrophilic polymer comprises at least one of polyvinyl alcohol, polyethylene glycol homopolymer or copolymer, polyacrylamide, polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, polyacrylic acid and its salt, polyacryloyloxyethyltrimethyl ammonium chloride, dimethylaminoethyl poly (meth) acrylate, maleic anhydride copolymer, maleic acid copolymer, fumaric acid copolymer, starch, gelatin, hydroxyethyl cellulose.
In one embodiment, the binder comprises a polymer or a monomer that synthesizes the polymer.
In one embodiment, the polymer comprises at least one of polyurethane, epoxy, polyacrylate.
The invention has the following beneficial effects:
according to the invention, the surface of the silicon rubber is treated, and then the first coating and the second coating comprising the antistatic agent and the binder are formed on the surface, the compatibility of the antistatic agent and the binder is good, the antistatic agent is formed on the surface of the silicon rubber through the first coating and the second coating, a permanent antistatic effect is achieved on the surface of the silicon rubber, and the mechanical property and the like of the silicon rubber are not influenced.
The first coating can ensure that low-molecular silicone oil in the silicone rubber is not easy to migrate to the surface of the silicone rubber, and can keep the surface performance of the silicone rubber. In addition, the multifunctional compound in the first coating can chemically react with the hydroxyl on the surface of the silicon rubber to form a stable chemical bond, so that the adhesive force between the first coating and the surface of the silicon rubber is improved. Meanwhile, the multifunctional compound can also perform chemical reaction with the binder in the second coating, so that the bonding strength of the first coating and the second coating is improved, and the silicone rubber has permanent antistatic property.
The colorless transparent antistatic silicone rubber can be prepared by mixing the colorless transparent antistatic agent and the colorless transparent adhesive with good compatibility to form the colorless transparent antistatic coating on the surface of the silicone rubber.
Detailed Description
The preparation method of the antistatic silicone rubber provided by the invention will be further explained below.
The preparation method of the antistatic silicone rubber provided by the invention comprises the following steps:
s1, providing a silicon rubber, and carrying out surface treatment on the silicon rubber to enable the surface of the silicon rubber to be provided with polar groups;
s2, coating a multifunctional compound on the surface of the silicone rubber with the polar group to form a first coating, and enabling the multifunctional compound to react with the polar group to form a chemical bond;
s3, coating an antistatic agent and a binder on the surface of the first coating to form a second coating, reacting the binder with the multifunctional compound to form a chemical bond, and curing to obtain the antistatic silicone rubber.
In step S1, there are many methods for surface-treating the silicone rubber, including a solvent treatment method, a coupling agent treatment method, a flame treatment method, an ultraviolet light irradiation treatment method, a plasma surface treatment method, and the like. When selecting the surface treatment method, the physicochemical properties of the silicone rubber and the actual production conditions need to be considered at the same time. Therefore, the silicone rubber is preferably surface-treated by an ultraviolet light irradiation treatment method or a plasma surface treatment method.
However, the surface treatment of silicone rubber by using the ultraviolet light irradiation treatment alone is inefficient. Therefore, the ultraviolet light irradiation treatment method of the present invention is preferably performed in an ozone atmosphere, and preferably, the concentration of ozone is 1ppm to 200 ppm. Ozone is photolyzed under the irradiation of ultraviolet light having a wavelength of 200nm to 300nm, preferably 254nm, to generate molecular oxygen, atomic oxygen, hydroxyl radical, and the like. The atomic oxygen or hydroxyl radical has strong oxidizing property and can oxidize Si-CH on the silicon rubber3Unstable intermediates are formed, which react further to form carbon dioxide, water and other volatile organics. Thus, after treatment in this manner, the silicon-methyl groups (Si-CH) on the polydimethylsiloxane may be converted3) Oxidized into silicon-hydroxyl (Si-OH) to form a layer of inorganic silicon dioxide, so that the surface of the silicon rubber is provided with a large amount of polar groups which can react, such as hydroxyl.
The wavelength range of the ultraviolet light is 10 nm-400 nm, the ozone can be generated by exciting oxygen molecules in situ by the ultraviolet light with the wavelength of 100 nm-200 nm, preferably the ultraviolet light with the wavelength of 185nm, the ozone can be introduced through additional equipment, pure oxygen can be introduced into a silicon rubber environment to improve the oxygen concentration in the environment, and the high-concentration ozone is generated in situ under the irradiation of the ultraviolet light with the wavelength of 100 nm-200 nm. Therefore, the wavelength of the ultraviolet light in the ultraviolet light irradiation treatment method is preferably 100nm to 300 nm.
Preferably, the temperature of the ultraviolet irradiation treatment method is 20-200 ℃, and the time is 1-120 minutes, so that the surface of the silicon rubber is fully treated.
Similarly, the plasma surface treatment method is performed in an oxygen atmosphere to improve treatment efficiency. The temperature of the plasma surface treatment method is 20-200 ℃, and the time is 1-120 minutes.
Plasma is a non-condensed system created by ionizing a gas (vapor) portion under specific conditions, consisting of neutral atoms or molecules, excited atoms or molecules, radicals, electrons or negative ions, positive ions, and radiation photons. In the plasma surface treatment process, when the plasma impacts the surface of the silicon rubber, the energy of the plasma is transferred to molecules on the surface layer of the silicon rubber, and the surface can be etched, so that molecules of gas or other substances adsorbed on the surface are analyzed. Using non-polymeric inorganic gases (Ar, N)2、H2、O2Etc.) to perform surface reaction, and excited molecules, free radicals and electron ions which participate in the surface reaction, and also includes the radiation effect of ultraviolet light generated by the plasma. Specific functional groups are introduced on the surface through surface reaction to generate surface erosion and form a cross-linked structure layer or generate polar groups such as-COOH, -OH and the like.
Furthermore, the equipment of the ultraviolet irradiation treatment method is relatively simple and cheap, is suitable for large-area treatment and has high efficiency. Therefore, it is preferable that the silicone rubber is surface-treated by an ultraviolet light irradiation treatment method, and the ultraviolet light irradiation treatment method is performed in an ozone atmosphere.
After the surface treatment of the silicone rubber, the surface contains a large number of polar groups which are hydrophilic and can easily react with other groups, such as hydroxyl, carbonyl, carboxyl and the like. Polar groups such as hydroxyl groups can chemically react with the compound, so that the bonding force of the surface of the silicon rubber can be enhanced.
In fact, the inorganic silica layer formed on the surface of the surface-treated silicone rubber is not continuous but is a mixture of inorganic silica having a sea-island structure and organosiloxane. Moreover, the inorganic silica layer on the surface of the treated silicone rubber is thin and has a thickness of only a few nanometers to a few tens of nanometers. Therefore, the low-molecular silicone oil in the silicone rubber is easy to migrate to the surface of the silicone rubber, and covers the inorganic silica layer, so that the surface of the silicone rubber loses polar groups and becomes a hydrophobic layer again.
Accordingly, a multifunctional compound is coated on the surface of the polar group-bearing silicone rubber to form a first coating layer through step S2. The multifunctional compound can be directly formed on the surface of the silicone rubber with the polar group by spraying, coating and the like, or can be formed on the surface of the silicone rubber with the polar group by spraying, coating and the like after being dissolved in water or an organic solvent to form a multifunctional compound solution.
After the multifunctional compound is coated on the surface of the silicone rubber with the polar group to form a continuous and compact first coating, the low-molecular silicone oil in the silicone rubber is not easy to migrate to the surface of the silicone rubber, and the surface performance of the silicone rubber can be maintained. In addition, the multifunctional compound in the first coating can chemically react with the hydroxyl on the surface of the silicon rubber to form a stable chemical bond, so that the adhesive force between the first coating and the surface of the silicon rubber is improved. Meanwhile, the multifunctional compound can also carry out chemical reaction with radicals on other substrates or other compounds, so that the bonding strength of the silicone rubber and other substrates is improved, or other compounds can be grafted on the surface of the first coating to achieve other surface effects.
Preferably, after the first coating layer is formed, the temperature is kept at 20-150 ℃ for 1-60 minutes, so that the multifunctional group compound in the first coating layer can fully and rapidly react with the polar group, and the solvent in the first coating layer can also be volatilized.
The multifunctional compound is at least one of silane coupling agent, polyisocyanate and multifunctional epoxy compound.
Wherein the chemical formula of the silane coupling agent is Y-R-SiX3Wherein Y is a non-hydrolyzable group including an alkenyl group (mainly vinyl group) and a terminal chloro group (-Cl), amino group (-NH)2) Mercapto (-SH), epoxyAzido (-N)3) Functional groups such as an isocyanate group (-NCO), a cationic group, etc.; r is a saturated or unsaturated hydrocarbon group; x is a hydrolyzable group including-Cl, -OMe, -OEt, -OC2H4OCH3、-OSiMe3And the like. Preferably, the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane (KH-550), gamma-glycidoxypropyltrimethoxysilane (KH-560), gamma- (methacryloyloxy) propyltrimethoxysilane (KH-570), 3- (2-aminoethyl) -aminopropyltrimethoxysilane (KH-792), N-aminoethyl-3-aminopropylmethyltrimethoxysilane (KH-602), 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane.
The polyisocyanate includes a compound containing three or more isocyanate groups, and specifically, the polyisocyanate includes at least one of triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, toluene diisocyanate dimer, toluene diisocyanate trimer, diphenylmethane-4, 4-diisocyanate, polyphenyl polymethylene polyisocyanate, and toluene diisocyanate-trimethylolpropane adduct.
The multifunctional epoxy compound comprises a compound containing three or more than three epoxy groups, and specifically, the multifunctional epoxy compound comprises at least one of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, polyglycerol triglycidyl ether, propoxyglycerol triglycidyl ether, glycerol triglycidyl ether, tetraglycidyl ether tetraphenylethane, triglycidyl ether triphenylmethane, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol and tetraglycidyl-m-xylylenediamine.
In step S3, the binder is not limited as long as it can react with the multifunctional compound to form a chemical bond, and includes a polymer or a monomer forming the polymer. Preferably, the polymer comprises at least one of polyurethane, epoxy resin and polyacrylate.
The polyurethane or the monomer for forming the polyurethane contains hydroxyl (-OH), isocyanate (-NCO) and other groups, and can react with functional groups on the multifunctional coating on the surface of the silicon rubber to form stable chemical bonds. The epoxy resin contains epoxy groups and hydroxyl groups, and can chemically react with functional groups on the multifunctional coating. The double bond contained in the polyacrylate can be copolymerized with a group such as a double bond in a polyfunctional group. For example, the epoxy group contained in the multifunctional coating can react with the hydroxyl, amino, isocyanate, and carboxyl groups on the adhesive layer; the amino group contained in the multifunctional coating can chemically react with the epoxy group, the isocyanate group, the double bond, the carboxyl group and other groups on the bonding layer; the double bonds contained on the multifunctional coating can chemically react with amino groups, double bonds and other groups on the bonding layer; the sulfydryl contained in the multifunctional coating can react with double bonds, isocyanate groups, carboxyl groups, epoxy groups and other groups on the bonding layer.
Preferably, the mixture of raw materials for synthesizing polyurethane, such as isocyanate, polyol, chain extender, cross-linking agent, catalyst and auxiliary agent, or polyurethane is used as a binder and is coated or sprayed on the surface of the first coating, the multifunctional compound of the first coating contains at least one group of epoxy group, amino group, mercapto group and isocyanate group, and the binder and the multifunctional compound react to form a stable chemical bond.
Preferably, the epoxy resin monomer, curing agent, auxiliary agent and other mixture or epoxy resin is used as a binder to be coated or sprayed on the surface of the first coating, the multifunctional compound of the first coating contains at least one group of epoxy group, amino group, mercapto group and isocyanate group, and the binder and the multifunctional compound react to form a stable chemical bond.
Preferably, the mixture of acrylate monomer, initiator, cross-linking agent and assistant or polyacrylate resin is used as binder to coat or spray on the surface of the first coating, the multifunctional compound of the first coating contains at least one group of double bond, mercapto group, epoxy group and isocyanate group, and the binder and the multifunctional compound react to form stable chemical bond.
When polymers such as polyester, polyacrylate, polyurethane and the like with double bonds at the end groups and a radical initiator or a photoinitiator are used as the binder, the multifunctional compound of the first coating contains double bonds. Under the heating or ultraviolet irradiation, the adhesive and the polyfunctional compound react to form a stable chemical bond.
Also, the antistatic agent is not limited, and may have a good compatibility with the binder. Including surfactants, hydrophilic polymers, inorganic salts, ionic liquids, carbon black, metals, metal oxides, and the like. Preferably, the antistatic agent is at least one of a surfactant or a hydrophilic polymer.
When the surfactant is used as an antistatic agent, molecules of the antistatic agent migrate outward to form an antistatic layer after being mixed with adhesive properties and forming a second coating layer. The lipophilic groups of the antistatic molecules are planted in the adhesive, and the hydrophilic groups are oriented and arranged on the air side. The former keeps certain compatibility between the antistatic agent and the binder, and the latter adsorbs water molecules in the air to form a layer of uniformly distributed conductive solution on the surface of the second coating or conducts surface charges by self ionization to achieve the antistatic effect. When the antistatic layer on the surface is lost or damaged, the antistatic agent molecules inside can continue to migrate outwards for supplement, so that the antistatic effect is continued.
Preferably, the surfactant comprises at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant; wherein the cationic surfactant comprises at least one of a quaternary ammonium salt surfactant, a morpholine hydrochloride surfactant or an imidazoline salt surfactant; the anionic surfactant comprises at least one of a sulfonate surfactant, a phosphate surfactant, or a carboxylate surfactant; the nonionic surfactant includes at least one of a surfactant comprising a polyoxyethylene segment or a polyol.
Further, the surfactant is a nonionic surfactant including at least one of a surfactant including a polyoxyethylene segment or a polyol.
When the hydrophilic polymer is used as antistatic agent, it can form alloy with adhesive to permanently maintain antistatic effect.
Preferably, the hydrophilic polymer is polyvinyl alcohol, polyethylene glycol homopolymer or copolymer, polyacrylamide, polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, polyacrylic acid and its salt, polyacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl poly (meth) acrylate, maleic anhydride copolymer, maleic acid copolymer, fumaric acid copolymer, starch, gelatin, hydroxyethylcellulose, or a polymer containing these polymer segments.
According to the invention, the surface of the silicon rubber is treated, and then the first coating and the second coating comprising the antistatic agent and the binder are formed on the surface, the compatibility of the antistatic agent and the binder is good, the antistatic agent is formed on the surface of the silicon rubber through the first coating and the second coating, a permanent antistatic effect is achieved on the surface of the silicon rubber, and the mechanical property and the like of the silicon rubber are not influenced.
In addition, the colorless transparent antistatic silicone rubber can be prepared by mixing the colorless transparent antistatic agent and the colorless transparent adhesive with good compatibility to form the colorless transparent antistatic coating on the surface of the silicone rubber.
The antistatic silicone rubber prepared by the invention can be used for preparing antistatic silicone rubber shoes, electronic device packaging materials, mobile phone shells, sealing rings, rubber rollers, keys and the like.
Hereinafter, the preparation method of the antistatic silicone rubber will be further illustrated by the following specific examples.
Example 1:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 10 minutes to obtain the surface-treated silicon rubber sample A1.
Preparing 1 part of 3-aminopropyltriethoxysilane, 5 parts of water and 94 parts of ethanol solution, and spraying the solution on the surface of the treated silicon rubber sample A1 with the spraying amount of 0.1g/cm2The solution was heated at 70 ℃ for 3 minutes to obtain silicone rubber B1 with a surface grafted with a reactive group.
Mixing the epoxy resin A glue and the epoxy resin B glue according to the proportion of 3:1, adding 2 wt% of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, uniformly mixing, coating on silicon rubber B1, and curing to obtain the antistatic silicon rubber 1.
Example 2:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the surface-treated silicon rubber sample A2.
Preparing 1 part of gamma-glycidoxypropyltrimethoxysilane, 5 parts of water and 94 parts of ethanol solution, spraying the solution on the surface of a treated silicon rubber sample A2, and heating at 70 ℃ for 3 minutes to obtain silicon rubber B2 with reactive groups grafted on the surface.
Mixing the epoxy resin A glue and the epoxy resin B glue according to the ratio of 3:1, adding 2 wt% of N-hexadecylpyridine nitrate, uniformly mixing, coating on the silicon rubber B2, and curing to obtain the antistatic silicon rubber 2.
Example 3:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the surface-treated silicon rubber sample A3.
Preparing 1 part of N-aminoethyl-3-aminopropyl methyl trimethoxy silane, 5 parts of water and 94 parts of ethanol solution, spraying the solution on the surface of a treated silicon rubber sample A3, and heating at 70 ℃ for 3 minutes to obtain silicon rubber B3 with reactive groups grafted on the surface.
And adding 2 wt% of dodecyl trimethyl ammonium chloride into the polyurethane prepolymer, uniformly mixing, coating the mixture on silicon rubber B3, and curing to obtain the antistatic silicon rubber 3.
Example 4:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the surface-treated silicon rubber sample A4.
Spraying triphenylmethane triisocyanate on the surface of the treated silicon rubber sample A4, and heating at 70 ℃ for 3 minutes to obtain silicon rubber B4 with reactive groups grafted on the surface.
Adding 2 wt% of sodium dilaurate phosphate into the polyurethane prepolymer, uniformly mixing, coating the mixture on silicon rubber B4, and curing to obtain the antistatic silicon rubber 4.
Example 5:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, simultaneously filling pure oxygen into the ultraviolet ozone cleaning machine, and irradiating for 60 minutes at the wavelength of 100-300nm in the ultraviolet irradiation process to obtain the surface-treated silicon rubber sample A5.
And spraying the blocked toluene diisocyanate-trimethylolpropane emulsion on the surface of the treated silicon rubber sample A5, and heating at 70 ℃ for 3 minutes to obtain the silicon rubber B5 with the surface grafted with the isocyanate group.
Adding 2 wt% of polyethylene glycol 4000 into the waterborne polyurethane pre-emulsion, uniformly mixing, coating on silicon rubber B5, and curing to obtain the antistatic silicon rubber 5.
Example 6:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 50 ℃, simultaneously filling pure oxygen into the ultraviolet ozone cleaning machine, and irradiating for 10 minutes at the wavelength of 100-300nm in the ultraviolet irradiation process to obtain the surface-treated silicon rubber sample A6.
Preparing 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane, 5 parts of water and 94 parts of ethanol solution, adding a small amount of acetic acid to adjust the pH value to 3-4, and spraying the solution on the surface of a treated silicon rubber sample sheet A6, wherein the spraying amount is 0.2g/cm2Solution to obtain the silicone rubber B6 with the surface grafted with isocyanate groups.
And (3) coating the mixed solution of polyurethane with an acrylate group at the end group and a photoinitiator on the surface of the silicon rubber B6, and irradiating and curing by ultraviolet light to obtain the antistatic silicon rubber 6.
Example 7:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 50 ℃, simultaneously filling pure oxygen into the ultraviolet ozone cleaning machine, and irradiating for 10 minutes at the wavelength of 100-300nm in the ultraviolet irradiation process to obtain the surface-treated silicon rubber sample A7.
Preparing 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane, 5 parts of water and 94 parts of ethanol solution, adding a small amount of acetic acid to adjust the pH value to 3-4, and spraying the solution on the surface of a treated silicon rubber sample sheet A7, wherein the spraying amount is 0.2g/cm2Solution to obtain the silicone rubber B7 with the surface grafted with isocyanate groups.
And (3) coating the mixed solution of acrylic acid, acrylic ester, a crosslinking agent, an initiator azobisisobutyronitrile and an antistatic agent trimethylhexadecyl ammonium acetate on the surface of the silicone rubber B7, and heating and curing at 70 ℃ to obtain the antistatic silicone rubber 7.
Example 8:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, simultaneously filling 1ppm of ozone into the ultraviolet ozone cleaning machine, and irradiating for 120 minutes under the condition that the wavelength of ultraviolet light is 100-300nm in the ultraviolet light irradiation process to obtain the surface-treated silicon rubber sample A8.
Preparing 1 part of tetraglycidyl diaminodiphenylmethane, 5 parts of water and 94 parts of ethanol solution, and spraying the solution on the surface of the treated silicon rubber sample A8 with the spraying amount of 0.2g/cm2And (4) obtaining the silicone rubber B8 with the surface grafted with epoxy groups.
Mixing the epoxy resin A glue and the epoxy resin B glue according to the proportion of 3:1, adding 2 wt% of N-hexadecyl pyridine nitrate, uniformly mixing, coating on silicon rubber B8, and curing to obtain the antistatic silicon rubber 8.
Example 9:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 120 ℃, simultaneously filling 200ppm of ozone into the ultraviolet ozone cleaning machine, and irradiating for 1 minute, wherein the wavelength of ultraviolet light is 100-300nm in the ultraviolet light irradiation process to obtain the silicon rubber sample A9 after surface treatment.
Preparing 2 parts of 3-mercaptopropyltrimethoxysilane, 5 parts of water and 93 parts of ethanol solution, and spraying the solution on the surface of the treated silicon rubber sample A9 with the spraying amount of 0.2g/cm2And (4) obtaining the silicone rubber B9 with the surface grafted with epoxy groups.
Preparing diphenylmethane diisocyanate (MDI), polyether polyol, a catalyst and a dimethylolpropionic acid binder, adding 1 wt% of dioctyl potassium dithiophosphate, uniformly mixing, coating on silicon rubber B9, and curing to obtain the antistatic silicon rubber 9.
Example 10:
the silicon rubber sample wafer is placed in a plasma processor, pure oxygen is introduced, the processing temperature is 20 ℃, and the silicon rubber sample wafer is processed for 120 minutes, so that the silicon rubber sample wafer A10 with the surface processed is obtained.
1 part of 3- (2-aminoethyl) -aminopropyltrimethoxysilane (KH-792), 5 parts of water and 94 parts of ethanol solution were prepared, and the solution was sprayed on the surface of a treated silicone rubber sample piece A10 in an amount of 0.1g/cm2The solution was heated at 70 ℃ for 3 minutes to obtain silicone rubber B10 with a surface grafted with a reactive group.
Mixing the epoxy resin A glue and the epoxy resin B glue according to the proportion of 3:1, adding 5 wt% of water-soluble polyoxyethylene ether alcohol modified silicone oil, uniformly mixing, coating on the silicone rubber B10, and curing to obtain the antistatic silicone rubber 10.
Example 11:
the silicon rubber sample wafer is placed in a plasma processor, pure oxygen is introduced, the processing temperature is 50 ℃, and the silicon rubber sample wafer is processed for 60 minutes, so that the silicon rubber sample wafer A11 with the surface processed is obtained.
Toluene is addedThe diisocyanate trimer solution was sprayed on the surface of the treated silicone rubber sample A11 in an amount of 0.1g/cm2The solution was heated at 70 ℃ for 3 minutes to obtain silicone rubber B11 with a surface grafted with a reactive group.
And (3) uniformly mixing 2 wt% of water-soluble polyoxyethylene ether alcohol modified silicone oil in the polyurethane prepolymer, coating the mixture on silicone rubber B11, and curing to obtain the antistatic silicone rubber 11.
Example 12:
the silicon rubber sample wafer is placed in a plasma processor, pure oxygen is introduced, the processing temperature is 120 ℃, and the silicon rubber sample wafer is processed for 1 minute to obtain a silicon rubber sample wafer A12 after surface treatment.
Preparing 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane, 5 parts of water and 94 parts of ethanol solution, adding a small amount of acetic acid to adjust the pH value to 3-4, and spraying the solution on the surface of a treated silicon rubber sample sheet A12, wherein the spraying amount is 0.2g/cm2Solution to obtain the silicone rubber B12 with the surface grafted with isocyanate groups.
And (3) coating the mixed solution of polyurethane resin with an acrylate group at the end group, a photoinitiator and 2 wt% of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate on the surface of the silicone rubber B12, and irradiating and curing by ultraviolet light to obtain the antistatic silicone rubber 12.
Comparative example 1:
and (3) placing the silicon rubber sample wafer in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the silicon rubber sample wafer 13 after surface treatment.
Comparative example 2:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the surface-treated silicon rubber sample A14.
Preparing 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane, 5 parts of water and 94 parts of ethanol solution, adding a small amount of acetic acid to adjust the pH value to 3-4, and spraying the solution on the surface of a treated silicon rubber sample sheet A14, wherein the spraying amount is 0.1g/cm2The solution was heated at 70 ℃ for 3 minutes to obtain a surface-coated silicone rubber 14.
Comparative example 3:
and (3) placing the silicon rubber sample in an ultraviolet ozone cleaning machine, wherein the temperature of the ultraviolet ozone cleaning machine is 20 ℃, the wavelength of ultraviolet light in the ultraviolet light irradiation process is 100-300nm, and irradiating for 60 minutes to obtain the surface-treated silicon rubber sample A15.
Preparing 1 part of 3-aminopropyltriethoxysilane, 5 parts of water and 94 parts of ethanol solution, and spraying the solution on the surface of the treated silicon rubber sample A15 with the spraying amount of 0.1g/cm2The solution was heated at 70 ℃ for 3 minutes to obtain silicone rubber B15 with a surface grafted with a reactive group.
Mixing the epoxy resin A glue and the epoxy resin B glue according to the ratio of 3:1, coating the mixture on silicon rubber B15, and curing to obtain the silicon rubber 15.
The silicone rubbers of examples 1 to 12 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the silicone rubbers obtained in examples 1 to 12 are all antistatic rubbers, while the silicone rubbers obtained in comparative examples 1 to 3 have poor antistatic properties.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (15)
1. The preparation method of the antistatic silicone rubber is characterized by comprising the following steps:
providing silicon rubber, and carrying out surface treatment on the silicon rubber to enable the surface of the silicon rubber to be provided with polar groups;
coating a multifunctional compound on the surface of the silicone rubber with the polar group to form a first coating, and reacting the multifunctional compound with the polar group to form a chemical bond;
and coating an antistatic agent and a binder on the surface of the first coating to form a second coating, reacting the binder with the polyfunctional compound to form a chemical bond, and curing to obtain the antistatic silicone rubber.
2. The method for preparing an antistatic silicone rubber according to claim 1, wherein the surface treatment method comprises an ultraviolet light irradiation treatment method or a plasma surface treatment method; wherein,
the ultraviolet light irradiation treatment method is performed in an ozone atmosphere;
the plasma surface treatment method is performed in an oxygen atmosphere.
3. The method for preparing antistatic silicone rubber according to claim 2, wherein the wavelength of the ultraviolet light in the ultraviolet light irradiation treatment method is 100nm to 300 nm; and/or
The temperature of the ultraviolet light irradiation treatment method is 20-200 ℃, and the time is 1-120 minutes.
4. The method for preparing antistatic silicone rubber according to claim 2, wherein the temperature of the plasma surface treatment process is 20 ℃ to 200 ℃ for 1 minute to 120 minutes.
5. The method for preparing antistatic silicone rubber according to claim 1, wherein the polar group is a hydroxyl group.
6. The method for preparing an antistatic silicone rubber according to claim 1, wherein the first coating layer is formed and then maintained at 20 to 150 ℃ for 1 to 60 minutes.
7. The method for preparing antistatic silicone rubber according to claim 1, wherein the multifunctional compound comprises at least one of a silane coupling agent, a polyisocyanate, and a multifunctional epoxy compound.
8. The method of claim 7, wherein the silane coupling agent comprises at least one of 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane.
9. The method of preparing antistatic silicone rubber according to claim 7, wherein the polyisocyanate comprises a compound containing three or more isocyanate groups.
10. The method according to claim 7, wherein the polyfunctional epoxy compound comprises a compound having three or more epoxy groups.
11. The method for preparing antistatic silicone rubber according to claim 1, wherein the antistatic agent comprises at least one of a surfactant and a hydrophilic polymer.
12. The method for preparing antistatic silicone rubber according to claim 11, wherein the surfactant comprises at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant; wherein,
the cationic surfactant comprises at least one of quaternary ammonium salt surfactant, morpholine hydrochloride surfactant or imidazoline salt surfactant;
the anionic surfactant comprises at least one of a sulfonate surfactant, a phosphate surfactant, or a carboxylate surfactant;
the nonionic surfactant includes at least one of a surfactant comprising a polyoxyethylene segment or a polyol.
13. The method of claim 11, wherein the hydrophilic polymer comprises at least one of polyvinyl alcohol, polyethylene glycol homopolymer or copolymer, polyacrylamide, polyhydroxyethyl acrylate, polyhydroxypropyl acrylate, polyacrylic acid and its salt, polyacryloyloxyethyltrimethyl ammonium chloride, dimethylaminoethyl poly (meth) acrylate, maleic anhydride copolymer, maleic acid copolymer, fumaric acid copolymer, starch, gelatin, hydroxyethyl cellulose.
14. The method for preparing antistatic silicone rubber according to claim 1, wherein the binder comprises a polymer or a monomer for synthesizing the polymer.
15. The method for preparing antistatic silicone rubber according to claim 14, wherein the polymer comprises at least one of polyurethane, epoxy resin, polyacrylate.
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| CN201811611915.0A CN110655669A (en) | 2018-06-28 | 2018-06-28 | Antistatic silicone rubber |
| CN201810686792.0A CN108929453A (en) | 2018-06-28 | 2018-06-28 | The preparation method of antistatic silicone rubber |
| CN201811223565.0A CN109320752A (en) | 2018-06-28 | 2018-06-28 | The preparation method of antistatic silicone rubber |
| EP18924955.0A EP3816215A4 (en) | 2018-06-28 | 2018-12-18 | Method for surface treatment of silicone rubber |
| PCT/CN2018/121794 WO2020000934A1 (en) | 2018-06-28 | 2018-12-18 | Method for surface treatment of silicone rubber |
| US17/035,684 US11713380B2 (en) | 2018-06-28 | 2020-09-29 | Method for surface treatment of silicone rubber |
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