US3627659A - Radiation treatment of halogen containing olefinically unsaturated esters - Google Patents
Radiation treatment of halogen containing olefinically unsaturated esters Download PDFInfo
- Publication number
- US3627659A US3627659A US743033A US3627659DA US3627659A US 3627659 A US3627659 A US 3627659A US 743033 A US743033 A US 743033A US 3627659D A US3627659D A US 3627659DA US 3627659 A US3627659 A US 3627659A
- Authority
- US
- United States
- Prior art keywords
- acid
- esters
- radiation
- olefinically unsaturated
- mrad
- 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.)
- Expired - Lifetime
Links
- 230000005855 radiation Effects 0.000 title claims description 25
- 150000002148 esters Chemical class 0.000 title abstract description 17
- 229910052736 halogen Inorganic materials 0.000 title abstract description 11
- 150000002367 halogens Chemical class 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000005865 ionizing radiation Effects 0.000 abstract 1
- -1 bromoisopropyl alcohol Chemical compound 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000004922 lacquer Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- MUKJDVAYJDKPAG-UHFFFAOYSA-N 2,3-dibromopropyl prop-2-enoate Chemical compound BrCC(Br)COC(=O)C=C MUKJDVAYJDKPAG-UHFFFAOYSA-N 0.000 description 2
- VNBVMEJAPNHJSI-UHFFFAOYSA-N 2,3-dichloropropyl prop-2-enoate Chemical compound ClCC(Cl)COC(=O)C=C VNBVMEJAPNHJSI-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- XNLVWARRDCVUBL-UHFFFAOYSA-N 7-hexadecynoic acid Chemical compound CCCCCCCCC#CCCCCCC(O)=O XNLVWARRDCVUBL-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IFABLCIRROMTAN-MDZDMXLPSA-N (e)-1-chlorooctadec-9-ene Chemical compound CCCCCCCC\C=C\CCCCCCCCCl IFABLCIRROMTAN-MDZDMXLPSA-N 0.000 description 1
- VHZXZXQRRWODBC-IWQZZHSRSA-N (e)-2-(bromomethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(\CBr)C(O)=O VHZXZXQRRWODBC-IWQZZHSRSA-N 0.000 description 1
- OKLWGALVQNNLCI-IWQZZHSRSA-N (e)-2-(chloromethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(\CCl)C(O)=O OKLWGALVQNNLCI-IWQZZHSRSA-N 0.000 description 1
- RQPPLOJSTOYTCP-UPHRSURJSA-N (z)-2,3-dichlorobut-2-enedioyl dichloride Chemical compound ClC(=O)C(\Cl)=C(\Cl)C(Cl)=O RQPPLOJSTOYTCP-UPHRSURJSA-N 0.000 description 1
- OKLWGALVQNNLCI-HNQUOIGGSA-N (z)-2-(chloromethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(/CCl)C(O)=O OKLWGALVQNNLCI-HNQUOIGGSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QRRZOBWADKAXKF-UHFFFAOYSA-N 1,2-dibromopropan-1-ol Chemical compound CC(Br)C(O)Br QRRZOBWADKAXKF-UHFFFAOYSA-N 0.000 description 1
- PPLRQCYFUAGBBY-UHFFFAOYSA-N 1-prop-2-enoyloxybutyl 3-oxobutanoate Chemical compound C=CC(=O)OC(CCC)OC(=O)CC(C)=O PPLRQCYFUAGBBY-UHFFFAOYSA-N 0.000 description 1
- FUUBQAHRAHGWEE-UHFFFAOYSA-N 2,2,3-trichlorobutan-1-ol Chemical compound CC(Cl)C(Cl)(Cl)CO FUUBQAHRAHGWEE-UHFFFAOYSA-N 0.000 description 1
- BJVAUAPBLDCULS-UHFFFAOYSA-N 2,3,3-trichloroprop-2-enamide Chemical compound NC(=O)C(Cl)=C(Cl)Cl BJVAUAPBLDCULS-UHFFFAOYSA-N 0.000 description 1
- WMUBNWIGNSIRDH-UHFFFAOYSA-N 2,3,3-trichloroprop-2-enoic acid Chemical compound OC(=O)C(Cl)=C(Cl)Cl WMUBNWIGNSIRDH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- OSCXYTRISGREIM-UHFFFAOYSA-N 2-chloroprop-2-en-1-ol Chemical compound OCC(Cl)=C OSCXYTRISGREIM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- GXAZFDDOJOCXLO-UHFFFAOYSA-N 3,3-dibromopropyl prop-2-enoate Chemical compound BrC(Br)CCOC(=O)C=C GXAZFDDOJOCXLO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-QPJJXVBHSA-N [(e)-3-chloroprop-1-enyl]benzene Chemical compound ClC\C=C\C1=CC=CC=C1 IWTYTFSSTWXZFU-QPJJXVBHSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- NVLHKSGUMYMKRR-UHFFFAOYSA-N dodeca-2,10-dienediamide Chemical compound NC(=O)C=CCCCCCCC=CC(N)=O NVLHKSGUMYMKRR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- CNPHCSFIDKZQAK-UHFFFAOYSA-N n-prop-2-enylprop-2-enamide Chemical compound C=CCNC(=O)C=C CNPHCSFIDKZQAK-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
Definitions
- Shurtleff ABSTRACT A process for the production of coatings, impregnations or bonds by polymerization and cross-linking of mixtures containing olefinically unsaturated esters containing halogen by means ofionizing radiation.
- This invention relates to a process for the production of cross-linked polymers by the action of high-energy radiation on substantially solvent-free polymerizable systems.
- the process serves in particular for the production of coatings, impregnations and bonds.
- high-energy radiation being the range of wave and corpuscular radiation usually so termed in the literature (cf. for example Rexer-Wuckel, Chemische Vera Weg Stoffen für energiereiche Strahlung” (Chemical changes brought about in substances by high-energy radiation) Leipzig 1965).
- the radiation sources in the methods which are of industrial interest are usually electron generators having accelerating potentials of more than 300 up to 500 kilovolts.
- the possibilities of using this process for curing lacquers are however very limited. Since the electrons move away from the accelerator in straight lines, only flat articles can be treated in a single passage.
- Narrow limits are also placed on the prior art methods by the lacquer raw materials. Since conventional lacquer raw materials used in such methods only cure satisfactorily within relatively narrow ranges of radiation intensity, zones of different degrees of cure are formed when uneven lacquered surfaces are irradiated because of the different distances from the discharge aperture of the accelerator and according to the angle of incidence of the radiation.
- the object of this invention is to provide a type of binder for coating, impregnating or bonding agents which are curable by means of high-energy radiation, the said binder type being satisfactorily curable with relatively small doses of radiation but tolerating a considerable excess beyond these minimal dosages.
- the requirements as regards hardness, gloss, toughness, bond strength, and resistance to chemical reagents and solvents which are made according to the state of the art on the coatings, impregnations and bonds obtained should at least be fulfilled.
- cross-linked polymers can be prepared with particular advantage by irradiating systems containing olefinically unsaturated polymerizable monomers with high-energy radiation by using polymerizable monomers which consist to the extent of to 90 percent, preferably from to 70 percent, by weight of polymerizable esters containing halogen.
- polymerizable monomers which consist to the extent of to 90 percent, preferably from to 70 percent, by weight of polymerizable esters containing halogen.
- monomers substantially free from solvents are irradiated.
- esters of a, B-unsaturated polymerizable carboxylic acids with chlorinated and/or brominated alcohols for example esters of bromoisopropyl alcohol, 2-bromoethanol, 1,2- dibromopropanol, trichloronitroisopropanol, 2,2,3- trichlorobutanol, 3,4-dibromobutanol-l, 2-chloroisobutyl alcohol, chlorotrimethyl carbinol, 3,3,4-trichloropentanol-(2), and 3-bromo-2-methylbutanol-(2) with acrylic acid, crotonic acid, methacrylic acid, cinnamic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, dihydromuconic acid, oleic acid, palmitolic acid and the like.
- esters of halogen-containing alcohols of the said type, of halogen-free alcohols and of alcohols containing functional groups such as carbon-carbon double bonds, nitro groups and the like, with polymerizable acids containing halogen, particularly those having three to six carbon atoms are also suitable, for example esters of 2-chloroacrylic acid-( l 3-chloroacrylic acid-( 1 3,3-dichloroacrylic acid-( 1 2,3-dichloroacrylic acid-(l), trichloroacrylic acid, 2-bromoacrylic acid-( 1), 2,3- dichloro-3-bromoacrylic acid-( 1), 2-chlorocrotonic acid-( 1 3-chlorocrotonic acid-( 1 2-bromocrotonic acid-( 1 3- chloro-2-ethylcrotonic acid-( 1 2-bromoundecene-(2z) acidl l palmitolic acid diiodide, bromocitraconic acid, chloroci
- bromomesaconic acid dibromomaleic acid, dichloromaleic acid, monochloroitaconic acid, dichloroitaconic acid, 2- chlorocinnamic acid, 3-chlorocinnamic acid and 4-chlorocinnamic acid.
- halogen compounds different from the esters may be advantageous to use, in admixture with the said esters, halogen compounds different from the esters; besides free halogen-substituted olefinically unsaturated polymerizable acids, for example compounds such as acrylyl chloride, methacrylyl chloride, crotonyl chloride, 2- chlorocrontonyl chloride-( 1 cinnamyl chloride, oleyl chloride, citraconyl dichloride, dichloromaleyl dichloride, cinnamic-gamma-bromopropylyamide, and trichloroacrylamide.
- free halogen-substituted olefinically unsaturated polymerizable acids for example compounds such as acrylyl chloride, methacrylyl chloride, crotonyl chloride, 2- chlorocrontonyl chloride-( 1 cinnamyl chloride, oleyl chloride, citracony
- the systems cross-linked by irradiation may contain (in addition to the said compounds) from [0 to 90 percent, preferably from 30 to percent, by weight of other polymerizable compounds
- These may be as a rule olefmically unsaturated monomers used in conventional free-radical initiated polymerizations, particularly esters of acrylic or methacrylic acid with alcohols having one to eight carbon atoms, vinylbenzenes such as styrene or vinyltoluene, nitriles of unsaturated carboxylic acids having three to six carbon atom such as methacrylonitrile and acrylonitrile, vinyl esters of aliphatic monocarboxylic acids having two to eight carbon atoms, such as vinyl acetate, vinyl propionate and vinyl pivalate, and olefins, particularly higher olefins such as n-hexene and 4-methylpentene-( l Improvement in the hardness, elasticity and solvent resistance of the polymers prepared by irradiation can
- allyl esters or N-allylamides of ethylenically unsaturated carboxylic acids having three to six carbon atoms or their oligomers or low molecular weight polymers, e.g. allyl acrylate, allyl methacrylate, and N-allylacrylamide, or low molecular weight acrylic polymers of such monomeric compounds, diesters or diamides of aliphatic diols or triols or diarninoalkanes and ethylenically unsaturated carboxylic acids having three to six carbon atoms, e.g.
- polyfunctional polymerizable compounds may make up an amount of up to 80 percent by weight of the system capable of being polymerized by irradiation, but as a rule the amount is from 5 to 50 percent by weight.
- the systems may if desired contain further additives, for example pigments, soluble dyes, optical brighteners, plasticizers, agents for promoting flow and gloss, chemical polymerization initiators (such as peroxides or azo compounds) or aging retardants.
- additives for example pigments, soluble dyes, optical brighteners, plasticizers, agents for promoting flow and gloss, chemical polymerization initiators (such as peroxides or azo compounds) or aging retardants.
- polymerized compounds for example conventional lacquer binding agents such as alkyl resins, aminopl'ast resins, phenolic resins, epoxy resins, colophony resins, drying oils, nondrying oils, cellulose derivatives, polyacrylates, polymethacrylates and the like, particularly in an amount of from 5 to 30 percent by weight with reference to the monomers.
- Curing of the polymerizable systems according to the invention may be carried out with electron rays having an energy of more than 0.1 megavolts and with X-rays and gamma-rays, i.e. electromagnetic radiation in the wavelength range of from to 10'" cm. Curing takes place in a surprisingly high degree even when air is present independently of the radiation dosage and of the dose rate, so that in contrast to prior art methods the risk of overexposure is practically nonexistent. With small doses of radiation of from about i to 3 Mrad at irradiation periods of 10 to minutes up to high doses of more than 20 to 30 Mrad with short irradiation periods (0.5 to 5 seconds), completely nontacky, hard, elastic and highly glossy coatings can be obtained.
- Doses of l to 10 Mrad at dose rates of about 1 to about 10 Mrad/second are preferred. It is advantageous to choose small thicknesses of coating layer (e.g. from 50 microns down to less than 1 micron). it is also possible however to completely cure relatively thick coatings or lacquers, e.g. in the range of 50 to 500 microns. irradiation curing of the systems is preferably carried out at temperatures of from 0 to 150 C. and particularly from 10 to 80 C.
- the polymerizable systems may be applied to any solid substrates, for example by spraying, brushing, pouring, rolling, knife-coating, flooding, dipping or impregnation.
- the said systems are especially suitable for the production of coatings, lacquerings, bonds and impregnations.
- a film having a thickness of 50 microns is drawn from a mixture of 7 parts of 2.3-dibromopropyl acrylate and 3 parts of tetra-(allyloxymethyl)-acetylenediurea by means of filmdrawing equipment onto a deep-drawing metal sheet and irradiated with an electron beam at 2 megavolts accelerating potential with a dose of i2 Mrad at a dose rate of 19 Mrad per minute.
- a nontacky glossy hard coating is obtained which adheres very well. its elasticity according to DIN 53, 156 is 5.4.
- EXAMPLE 2 A deep-drawing metal sheet having a thickness of 0.7 mm. is coated on both sides by dipping it in a mixture of 3 parts of 2,3-dibromopropyl acrylate and 3 parts of tetra-( allyloxymethyl)-acetylenediurea and then exposed in the air at 30 C.
- a dose rate of 0.1 Mrad per minute an irradiation period of 20 minutes is necessary to obtain both on the side of the sheet facing the radiation source and on the opposite side a hard, glossy, elastic and well-adhering solvent-resistant coating.
- EXAMPLE 3 A mixture of 8 parts of tricyclodecenyl acrylate and 2 parts of 2,3-dichloropropyl acrylate is sprayed onto a deep-drawing metal sheet with a spray gun and irradiated for 2 minutes with an electron beam at an accelerating potential of 2 megavolts and a dose rate of 6 Mrad per minute. A nontacky hard colorless glossy film is obtained which does not dissolve in the usual solvents.
- EXAMPLE 4 A film having a thickness of 60 microns is drawn from a mixture of parts of 3a,4,5,6,7,7a-hexahydro-4,7- methanoindenyl acrylate-(5), 10 parts of 2,3-dichloro-3- bromoacrylic acid-( 1) and 10 parts of 2-chloroallyl acrylate by means of film-drawing equipment onto a plywood board and irradiated with an electron beam at an accelerating potential of 2 megavolts with a dose of 6 Mrad at a dose rate of l8 Mrad per minute. A glossy nontacky hard coating is obtained.
- EXAMPLE 6 The 30 percent solution of a copolymer prepared from 50 parts of butanediol acrylate acetylacetate, 43 parts of methyl methacrylate and 7 parts of n-butyl acrylate in a mixture of 12 parts of 2-chlorocrotonyl chloride-( 1 20 parts of 2,3- dichloropropyl acrylate and 68 parts of triallyl cyanurate is applied in a layer 50 microns in thickness to a deep-drawing metal sheet by knife-coating and irradiated with an electron beam at an accelerating potential of 2 megavolts with a dose of 12 Mrad at a dose rate of 18 Mrad per minute. A nontacky hard glossy insoluble coating is obtained.
- a process for the production of cross-linked polymers by irradiating with doses of high-energy radiation of from 1 to 30 Mrad at an irradiation period of from 0.5 seconds to 20 minutes a system containing (a) tetra-(allyloxymethyD- acetylenediurea, and (b)2,3-dibromopropyl acrylate.
- a process as in claim 1 wherein the high-energy radiation dose is from 20 to 30 Mrad at an irradiation period of from 0.5 to 5 seconds.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19671720283 DE1720283A1 (de) | 1967-07-11 | 1967-07-11 | Verfahren zur Herstellung von vernetzten Polymerisaten |
Publications (1)
Publication Number | Publication Date |
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US3627659A true US3627659A (en) | 1971-12-14 |
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ID=5689762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US743033A Expired - Lifetime US3627659A (en) | 1967-07-11 | 1968-07-08 | Radiation treatment of halogen containing olefinically unsaturated esters |
Country Status (2)
Country | Link |
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US (1) | US3627659A (no) |
GB (1) | GB1226657A (no) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4133907A (en) * | 1973-11-05 | 1979-01-09 | Texas Instruments Incorporated | High resolution electron beam resist |
US4250214A (en) * | 1976-02-23 | 1981-02-10 | The Dow Chemical Company | Wood-polymer composite containing a dicyclopentenyl acrylate or methacrylate polymer |
US4263372A (en) * | 1976-05-19 | 1981-04-21 | Rohm And Haas Company | Method of coating and/or impregnating porous substrates, and products obtained thereby |
US4307155A (en) * | 1976-02-23 | 1981-12-22 | The Dow Chemical Co. | Process of making wood-polymer composite containing a dicyclopentenyl acrylate or methacrylate polymer and composite |
US4400413A (en) * | 1980-08-29 | 1983-08-23 | Rohm And Haas Company | Acrylic polymer concrete compositions |
US4460625A (en) * | 1981-07-16 | 1984-07-17 | Rohm And Haas Company | Method of coating and impregnating concrete substrates, and products obtained thereby |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52108434A (en) * | 1976-03-08 | 1977-09-10 | Rohm & Haas | Aqueous coating composite |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2921006A (en) * | 1952-06-03 | 1960-01-12 | Gen Electric | Polymerization with high energy electrons |
US3213072A (en) * | 1961-08-07 | 1965-10-19 | American Cyanamid Co | Chlorination product of methylmethacrylate |
US3255163A (en) * | 1963-08-22 | 1966-06-07 | Thiokol Chemical Corp | Halo butenyl acrylates and polymers thereof |
-
1968
- 1968-07-08 US US743033A patent/US3627659A/en not_active Expired - Lifetime
- 1968-07-10 GB GB1226657D patent/GB1226657A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2921006A (en) * | 1952-06-03 | 1960-01-12 | Gen Electric | Polymerization with high energy electrons |
US3213072A (en) * | 1961-08-07 | 1965-10-19 | American Cyanamid Co | Chlorination product of methylmethacrylate |
US3255163A (en) * | 1963-08-22 | 1966-06-07 | Thiokol Chemical Corp | Halo butenyl acrylates and polymers thereof |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4133907A (en) * | 1973-11-05 | 1979-01-09 | Texas Instruments Incorporated | High resolution electron beam resist |
US4250214A (en) * | 1976-02-23 | 1981-02-10 | The Dow Chemical Company | Wood-polymer composite containing a dicyclopentenyl acrylate or methacrylate polymer |
US4307155A (en) * | 1976-02-23 | 1981-12-22 | The Dow Chemical Co. | Process of making wood-polymer composite containing a dicyclopentenyl acrylate or methacrylate polymer and composite |
US4263372A (en) * | 1976-05-19 | 1981-04-21 | Rohm And Haas Company | Method of coating and/or impregnating porous substrates, and products obtained thereby |
US4400413A (en) * | 1980-08-29 | 1983-08-23 | Rohm And Haas Company | Acrylic polymer concrete compositions |
US4460625A (en) * | 1981-07-16 | 1984-07-17 | Rohm And Haas Company | Method of coating and impregnating concrete substrates, and products obtained thereby |
Also Published As
Publication number | Publication date |
---|---|
GB1226657A (no) | 1971-03-31 |
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