NO773601L - ARTIC RESIN COMPONENTS FOR THE MANUFACTURE OF BIOCIDE COATINGS - Google Patents
ARTIC RESIN COMPONENTS FOR THE MANUFACTURE OF BIOCIDE COATINGSInfo
- Publication number
- NO773601L NO773601L NO773601A NO773601A NO773601L NO 773601 L NO773601 L NO 773601L NO 773601 A NO773601 A NO 773601A NO 773601 A NO773601 A NO 773601A NO 773601 L NO773601 L NO 773601L
- Authority
- NO
- Norway
- Prior art keywords
- compounds
- triorganotin
- glycidyl
- hardeners
- production
- Prior art date
Links
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 title claims description 7
- 239000011347 resin Substances 0.000 title claims description 7
- 239000003139 biocide Substances 0.000 title description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title 1
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 39
- 239000004848 polyfunctional curative Substances 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- -1 stannyl ester Chemical class 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 239000000057 synthetic resin Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000003822 epoxy resin Substances 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 16
- 239000003973 paint Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 12
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 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 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical class C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 2
- YSUXTNDMKYYZPR-UHFFFAOYSA-M tributylstannyl prop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C=C YSUXTNDMKYYZPR-UHFFFAOYSA-M 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-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
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RCXHRHWRRACBTK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propane-1,2-diol Chemical compound OCC(O)COCC1CO1 RCXHRHWRRACBTK-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AQFLJCURVBBBFN-UHFFFAOYSA-N OC(O)(O)C(C1CO1)(C1=CC=CC=C1)OC(C1CO1)(C(O)(O)O)C1=CC=CC=C1 Chemical class OC(O)(O)C(C1CO1)(C1=CC=CC=C1)OC(C1CO1)(C(O)(O)O)C1=CC=CC=C1 AQFLJCURVBBBFN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- JCYTYSQYTAVAPU-UHFFFAOYSA-N [4-[[[4-(hydroxymethyl)phenyl]-(oxiran-2-yl)methoxy]-(oxiran-2-yl)methyl]phenyl]methanol Chemical compound C1=CC(CO)=CC=C1C(C1OC1)OC(C=1C=CC(CO)=CC=1)C1OC1 JCYTYSQYTAVAPU-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 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
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical class OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013265 extended release Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- NHGVZTMBVDFPHJ-UHFFFAOYSA-N formyl fluoride Chemical class FC=O NHGVZTMBVDFPHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 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
- KJGLZJQPMKQFIK-UHFFFAOYSA-N methanolate;tributylstannanylium Chemical compound CCCC[Sn](CCCC)(CCCC)OC KJGLZJQPMKQFIK-UHFFFAOYSA-N 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000013406 prebiotics Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000003638 stannyl group Chemical group [H][Sn]([H])([H])* 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
Classifications
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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Abstract
Kunstharpikskomponenter for fremstilling av biocide belegg.Synthetic resin components for the production of biocidal coatings.
Description
Biocid virkende belegg skal i grenseflaten mellom belegg og omgivelse (havvann, ferskvann, jord, luft) avgi'en tilstrekkelig konsentrasjon av biocide stoffer som forhindrer angrep eller odeleggelse av de gjenstander som sokes beskyttet fra dyriske og vegetabilske organismer. Man må imidlertid unngå at det ved for store konsentrasjoner av aktivt stoff på overflaten av beleggene, som skyldes en for hoy opplosnings- eller avgivelses-hastighet for de biocide stoffene, belaster omgivelsene for sterkt og at beleggets virkning oppbrukes for tidlig. A biocidal coating must emit a sufficient concentration of biocidal substances at the interface between the coating and the environment (seawater, fresh water, soil, air) which prevents attack or destruction of the objects that are sought to be protected from animal and vegetable organisms. However, it must be avoided that in the case of excessive concentrations of active substance on the surface of the coatings, which is due to a too high dissolution or release rate for the biocidal substances, the environment is too heavily burdened and that the effect of the coating is used up too early.
Det er kjent å tilsette maling- og belegg-systemer kobber eller kobbersalter og metallorganiske forbindelser. It is known to add copper or copper salts and organometallic compounds to paint and coating systems.
Således brukes organotinnforbindelser og særlig triorganotinnforbindelser som tributyltinnoksid eller tributyltinnfluorid på grunn av deres fremragende mikrobiocide virkning i stort omfang bl.a. i desinfeksjonsmidler, som trebeskyttelses- og tekstil-beskyttelsesmiddel, og i fungecide og baktericide belegg og malinger, på basis av forskjellige bindemidler. Thus, organotin compounds and especially triorganotin compounds such as tributyltin oxide or tributyltin fluoride are used on a large scale due to their excellent microbiocidal effect, e.g. in disinfectants, as a wood preservative and textile preservative, and in fungicidal and bactericidal coatings and paints, based on various binders.
Et av de viktigste anvendelsesområder er for tiden under-vannsbeskyttelse av skip og sjokonstruksjoner mot bevoksning med sjoorganismer. One of the most important areas of application is currently the underwater protection of ships and sea structures against growth of marine organisms.
Hos skip bevirker f.eks. angrep på undervannsskroget med ballanider en kraftig okning i vannmotstanden som forer til oket' drivstoffforbruk, i mange tilfeller over ^ o%. In ships, e.g. attack on the underwater hull with ballanids a sharp increase in water resistance which leads to increased fuel consumption, in many cases over ^ o%.
Enkelte sjoorganismer kan angripe skipsmålingen og folgenCertain marine organisms can attack the ship measurement and the convoy
er oket metallkorrosjon.is increased metal corrosion.
Fjerning av undervannsbelegg i dokk er langvarig og kostbar Removal of underwater coatings in docks is lengthy and expensive
og forårsaker lengre avbruddstider.and cause longer outage times.
Den kjente og fremragende vannbestandighet hos epoxyharpikser,, deres ytterst ringe vannsvelling og hoye mekaniske styrke forte til at disse ble brukt som undervannsmalinger. Med tilsetning av triorganotinnforbindelser som tributyltinnfluorid, tributyltinnoksyd og tributiltinnsulfid får man meget effektive grohindrende malinger. The well-known and outstanding water resistance of epoxy resins, their extremely low water swelling and high mechanical strength led to these being used as underwater paints. With the addition of triorganotin compounds such as tributyltin fluoride, tributyltin oxide and tributyltin sulphide, very effective antifouling paints are obtained.
Disse systemer oppviser riktignok gode grohindrende egen-skaper, men har også visse ulemper som innskrenker deres anvendelse.. Enkelte triorganotinnforbindelser som tributyltinnoksyd er f.eks. lite f or en lic med epoxyharpiks-blndemidler. De avgis for hurtig på overflaten og virketiden for slike malinger er derfor ikke tilfredsstillende. These systems do indeed exhibit good anti-germ properties, but also have certain disadvantages which limit their use. Certain triorganotin compounds such as tributyltin oxide are e.g. little f or en lic with epoxy resin mixing agents. They are released too quickly on the surface and the working life of such paints is therefore not satisfactory.
I andre systemer tilsettes bindemidlene tilstrekkelig vann-opploselige pigmenter, metallsalter og inerte fyllstoffer. In other systems, sufficient water-soluble pigments, metal salts and inert fillers are added to the binders.
Opplosnings- eller utlosningsprosessen er imidlertid avhengig av så mange og forandrerlige faktorer (som f.eks. temperatur, underlag, vannets saltgehalt) at prosessen forloper ukontrollert. Som regel ligger overflatekonsentrasjonen av biocide stoffer for nymålinger langt over den nodvendige grensen og avgis derfor for tidlig til omgivelsene med den folge at den biocide effekt relativt snart uttommes. However, the dissolution or leaching process depends on so many and changeable factors (such as temperature, substrate, water salinity) that the process proceeds uncontrolled. As a rule, the surface concentration of biocidal substances for new measurements is far above the necessary limit and is therefore released too early into the environment, with the result that the biocidal effect is depleted relatively soon.
Man har i henhold til oppfinnelsen stilt seg den oppgave å avhjelpe disse ulempene og fremskaffe biocide belegg og malinger som er virksomme over et lengre tidsrom. According to the invention, one has set himself the task of remedying these disadvantages and providing biocidal coatings and paints which are effective over a longer period of time.
Oppgaven loses i henhold til oppfinnelsen ved hjelp av kunstharpiksblandinger av The task is solved according to the invention by means of synthetic resin mixtures of
1. Glycidylforbindelser av den typen som er vanlige for fremstillinger av polyaddukter,karakterisert vedgrupper med generell formel 1. Glycidyl compounds of the type that are common for the preparation of polyadducts, characterized by groups of general formula
hvor R betegner en eventuell substituert alifatisk, where R denotes an optionally substituted aliphatic,
cycloalifatisk eller aromatisk hydrocarbonrest med 1 til 10 C atomer, fortrinnsvis 3 - 6 C atomer, og cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 C atoms, preferably 3 to 6 C atoms, and
II. amino-gruppe-holdige herdere for glycidylforbindelsehe, inneholdende minst to aktive aminohydrogenatomer, nemlig bestående av II. amino group-containing hardeners for glycidyl compounds, containing at least two active amino hydrogen atoms, namely consisting of
a) 1. Omsetningsprodukter av hydroxyl-gruppe holdige primære eller sekundære di- eller polyaminoforbindelser med a) 1. Reaction products of hydroxyl-group containing primary or secondary di- or polyamino compounds with
2. Triorganotinnoksyder eller triorganotinnalkoksyder eller 2. Triorganotin oxides or triorganotin alkoxides or
b) addisjonsprodukter avb) addition products of
1. di- eller polyaminoforbindelser på1. di- or polyamino compounds on
2. stannylester - a ,(3-umettede carbonsyrer2. stannyl ester - a, (3-unsaturated carboxylic acids
samt eventueltas well as possibly
III. vanlige modifiseringsmidler som fyllstoffer, forsterkningsmidler, akseleratorer, pigmenter, for fremstilling av biocide belegg hvor de forbindelser som er nevnt under I og II helt eller delvis kan erstattes av tilsvarende organotinnfrie glycidylforbindelser, III. common modifiers such as fillers, reinforcing agents, accelerators, pigments, for the production of biocidal coatings where the compounds mentioned under I and II can be replaced in whole or in part by corresponding organotin-free glycidyl compounds,
henholdsvis herdere.respectively hardeners.
En annen gjenstand for oppfinnelsen er blandingskomponenter for anvendelse i henhold til krav 1, bestående av Another object of the invention is mixture components for use according to claim 1, consisting of
1. I. Glycidylforbindelser av den typen som er vanlig for fremstilling av polyaddukter, karkterisert ved grupper med generell formel - 0 - SnR^1. I. Glycidyl compounds of the type usual for the preparation of polyadducts, characterized by groups of general formula - 0 - SnR^
hvor R betegner en eventuell substituert alifatisk cycloalifatisk eller aromatisk hydroc.arbonrest med 1 til lo C atomer fortrinnsvis 3 - 6 C atomer, og where R denotes a possibly substituted aliphatic cycloaliphatic or aromatic hydrocarbon residue with 1 to 10 C atoms, preferably 3 to 6 C atoms, and
II. amino-gruppe holdige herdere for glycidylforbindelser, inneholdene minst to aktive aminohydrogenatomer nemlig av II. amino-group containing hardeners for glycidyl compounds, containing at least two active amino hydrogen atoms namely av
a) 1. omsetningsprodukter av hydroxyl-gruppe-holdige, primære eller sekundære di- eller a) 1. turnover products of hydroxyl-group-containing, primary or secondary di- or
polyaminoforbindelser medpolyamino compounds with
2. triorganotinnoksyder eller triorganotinnalkoksyder eller 2. triorganotin oxides or triorganotin alkoxides or
b) addisjonsprodukter avb) addition products of
1. di- eller polyaminoforbindelser på1. di- or polyamino compounds on
2. stannylester et ,[3-umettede carbonsyrer.2. stannyl esters and ,[3-unsaturated carboxylic acids.
2. En annen gjenstand for foreliggende oppfinnelse er en fremgangsmåte for fremstilling av glycidylforbindelser i henhold til krav 1 I,karakterisert vedat hydroxyl-gruppe-holdige glycidylforbindelser omsettes med triorganotinnforbindelser. 3. Ennå en gjenstand for oppfinnelsen er en fremgangsmåte for fremstilling av aminogruppeholdige herdere for glycidylforbindelser som angitt i krav 1 II,karakterisert vedat 2. Another object of the present invention is a method for producing glycidyl compounds according to claim 1 I, characterized in that hydroxyl group-containing glycidyl compounds are reacted with triorganotin compounds. 3. Another object of the invention is a method for producing amino group-containing hardeners for glycidyl compounds as stated in claim 1 II, characterized in that
a) 1. Hydroxyl-gruppe holdige primære eller sekundære di- eller polyaminoforbindelser omsettes med a) 1. Hydroxyl group-containing primary or secondary di- or polyamino compounds are reacted with
2. triorganotinnoksyder eller triorganotinnalkoksyder2. triorganotin oxides or triorganotin alkoxides
elleror
b) 1. di- eller polyaminoforbindelser adderes påb) 1. di- or polyamino compounds are added
2. stannylester a,b-umettede carbonsyrer.2. stannyl ester a,b-unsaturated carboxylic acids.
Ved kjemisk binding av organotinnrester i henhold til foreliggende oppfinnelse, enten via herderen og/eller via epoxyharpiksen, kan virkningen av nevnte malinger forlenges vesentlig. Den kjemiske binding av organotinnrestene bevirker en langsom og regulert avgivelse av den virksomme organotinnforbindelse siden de organotinnrester som er innbygget i den polymere forst må avspaltes under hydrolyse for disse restene kan komme til overflaten av malingen ved diffusjons-og opplosningsprosesser og utove den biocide virkning på overfalten. Man oppnår på denne måten en forlenget avgivelsestid av virksomt stoff med derav folgende forlenget virketid for malingen. By chemically binding organotin residues according to the present invention, either via the hardener and/or via the epoxy resin, the effect of said paints can be significantly extended. The chemical binding of the organotin residues causes a slow and regulated release of the active organotin compound, since the organotin residues that are built into the polymer must first be split off during hydrolysis, because these residues can come to the surface of the paint by diffusion and dissolution processes and exert the biocidal effect on the surface . In this way, an extended release time of active substance is achieved, with a consequent extended working time for the paint.
Belegg og malinger i henhold til oppfinnelsen har dessuten den fordel i. forhold til slike som er tilsatt triorganotinnforbindelser ved vanlig blanding at de lukter mindre. Av denne grunn kan malingene også brukes i baktericide og fungecide belegg og malinger interiort. Coatings and paints according to the invention also have the advantage compared to those to which triorganotin compounds have been added in the usual mixture that they smell less. For this reason, the paints can also be used in bactericidal and fungicidal coatings and interior paints.
For omsetningen med triorganotinnoksyder eller triorganotinnalkoksyder til organotinnholdige epoxyharpikser i henhold til oppfinnelsen kan man bruke alle hydroksyl-guppe-holdige epoxyforbindelser som lar seg herde med aminogruppe-holdige herdere ved romtemperatur eller noe forhoyet temperatur. For the conversion with triorganotin oxides or triorganotin alkoxides to organotin-containing epoxy resins according to the invention, all hydroxyl-group-containing epoxy compounds that can be cured with amino group-containing hardeners at room temperature or a slightly elevated temperature can be used.
Eksempler er vanlige epoxyharpikser som omsettes i henholdExamples are ordinary epoxy resins which are converted according to
til folgende generelle ligning: to the following general equation:
hvor R har ovennevnte betydning, men særlig betegner en butylrest, R"'" betegner en eventuelt forgrenet alifatisk hydrocarbonrest med where R has the above meaning, but in particular denotes a butyl residue, R"'" denotes an optionally branched aliphatic hydrocarbon residue with
1 - 6 C atomer, n er lik o,l til 20. CH~1 - 6 C atoms, n is equal to o,l to 20. CH~
og kan dessuten være 1,1 bis-C+-hydroxyf enyl) -ethan, bis-C^f-hydroxyfenyl)-methan, bis-C+-hydroxyfenyl)-sulfon, resorcin, hydrochinon eller novolakker. En omfangsrik rekke av egnede di-eller polyfenoler finner man i håndboken "Epoxidverbindungen und Epoxidharze" (Epoxyforbindelser og epoxyharpikser) av A.M. Paquin, Springer Verlag Berlin/Gottingen/Heidelberg, 1958. X-^og X^ kan and can also be 1,1 bis-C+-hydroxyphenyl)-ethane, bis-C+-hydroxyphenyl)-methane, bis-C+-hydroxyphenyl)-sulfone, resorcin, hydroquinone or novolaks. An extensive list of suitable di- or polyphenols can be found in the handbook "Epoxidverbindungen und Epoxidharze" (Epoxy compounds and epoxy resins) by A.M. Paquin, Springer Verlag Berlin/Gottingen/Heidelberg, 1958. X-^and X^ can
og andre rester av alifatiske, cyc.loalifatiske eller aromatiske dicarbonsyrer. Man kan bruke epoxyharpikser hvor X^= J.^eller X-^ er forskjellig fra X^. and other residues of aliphatic, cycloaliphatic or aromatic dicarboxylic acids. You can use epoxy resins where X^= J.^or X-^ is different from X^.
Ved omsetningen av alifatiske polyoller med epiklorhydrin til alifatiske glycidyletere dannes det ved bestemte reaksjons-^forhold hydroxylgruppeholde produkter. In the reaction of aliphatic polyols with epichlorohydrin to aliphatic glycidyl ethers, products containing hydroxyl groups are formed under certain reaction conditions.
Hydroxylgruppene kan omsettes med R^SnOR^" eller (R^Sn^O til epoxyharpikser ifolge oppfinnelsen. Som polyoller kan man bruke glycerol, pentaerythritol, trimethylolpropan eller erythritol etc. The hydroxyl groups can be converted with R^SnOR^" or (R^Sn^O) into epoxy resins according to the invention. Glycerol, pentaerythritol, trimethylolpropane or erythritol etc. can be used as polyols.
Som utgangsforbindelser på epoxyharpikssiden for fremstilling av biocide belegg kan man videre på egnet måte bruke glycidylethere av hydroxyalkylerte og fortrinnsvis hydroxymethylerte di- eller polyfenoler. Som eksempler nevnes: 2^-bis-Chydroxymethyl-^-hydroxyfenyl)-propan Glycidyl ethers of hydroxyalkylated and preferably hydroxymethylated di- or polyphenols can also be suitably used as starting compounds on the epoxy resin side for the production of biocidal coatings. Examples include: 2^-bis-Chydroxymethyl-^-hydroxyphenyl)-propane
2-(3-hydroxymethyl-1+-hydroxyf enyl) -2-(1+-hydroxyf enyl) -propan 2-(hydroxymethyl)-1,^-dihydroxybenzol 2-(3-hydroxymethyl-1+-hydroxyphenyl)-2-(1+-hydroxyphenyl)-propane 2-(hydroxymethyl)-1,^-dihydroxybenzol
2,6-di-hydroxymethyl-l,<>>+-dihydroxybenzol 2,6-di-hydroxymethyl-1,<>>+-dihydroxybenzene
Mono-hydroxymethyl-^- , h 1 -dihydroxyf enylether Mono-hydroxymethyl-^- , h 1 -dihydroxyphenyl ether
bis-Chydroxymethyl-^-hydroxyfenyl)-methanbis-C hydroxymethyl-^-hydroxyphenyl)-methane
hydroxymethylerte fluor-formaldehyd-harpikser.hydroxymethylated fluoro-formaldehyde resins.
De nevnte forbindelser kan fremstilles på kjent måte idet fenolene omsettes i nærvær av alkali ved ho til r/ o°C med vanndig formaldehydopplosning. Andre brukbare di- eller polyfenoler finner man i den nevnte litteratur (A.M. Paquin). The aforementioned compounds can be prepared in a known manner, as the phenols are reacted in the presence of alkali at ho to r/o°C with aqueous formaldehyde solution. Other usable di- or polyphenols can be found in the aforementioned literature (A.M. Paquin).
Overforingen av hydroxyalkylerte fenoler til hydroxyalkylerte fenylglycidylethere skjer på kjent måte ved omsetning med et overskudd av epiklorhydrin (i forhold til equivalente fenoliske OH-grupper) og equimolare mengder alkali. The conversion of hydroxyalkylated phenols to hydroxyalkylated phenylglycidyl ethers takes place in a known manner by reaction with an excess of epichlorohydrin (relative to equivalent phenolic OH groups) and equimolar amounts of alkali.
Den fremstilte glycidylether omsettes i et organisk opp-losningsmiddel med (R^Sn)^0 eller R^SnOR"<1>"slik at det pr. mol hydroxymethyl foreligger 0,01 - 1,0 mol R^Sn-grupper. The glycidyl ether produced is reacted in an organic solvent with (R^Sn)^O or R^SnOR"<1>" so that per mol of hydroxymethyl there are 0.01 - 1.0 mol of R^Sn groups.
Som bæresubstans for R^Sn-restene kan man også bruke mono-funksjonelle glycidylforbindelser. Eksempler er mono-, di- eller trihydroxymethyl-fenylglycidylethere eller blandinger av disse, mono- eller dihydroxymethylerte alkylsubstituerte fenylglycidylethere hvor alkyl-gruppen kan inneholde 1 - 9 C atomer. Forbindelser av denne typen tilsettes tinnholdige eller tinnfrie diglycidylethere eller .- estere etter omsetningen med trialkyltinnoksyder eller trialkyltinnalkoksyder, som for en reaktiv fortynner. Mono-functional glycidyl compounds can also be used as carriers for the R^Sn residues. Examples are mono-, di- or trihydroxymethyl-phenylglycidyl ethers or mixtures of these, mono- or dihydroxymethylated alkyl-substituted phenylglycidyl ethers where the alkyl group can contain 1 - 9 C atoms. Compounds of this type are added to tin-containing or tin-free diglycidyl ethers or esters after the reaction with trialkyltin oxides or trialkyltin alkoxides, as for a reactive diluent.
Til denne gruppen horer også de trialkyltinnglycidylethere som'kan fremstilles■av glycidol og beslektede forbindelser med trialkyltinnoksyder .eller - alkoksyder. This group also includes the trialkyltin glycidyl ethers which can be prepared from glycidol and related compounds with trialkyltin oxides or alkoxides.
Til fremstilling av egnede organotinnholdige herdere kanFor the production of suitable organotin-containing hardeners can
man omsette hydroxylalkylaminer med triorganotinnoksyder eller triorganotinnalkoksyder. Egnede hydroxyalkylaminer dannes ved one reacts hydroxylalkylamines with triorganotin oxides or triorganotin alkoxides. Suitable hydroxyalkylamines are formed by
omsetning av mono- eller diepoxyforbindelser med di- eller polyaminer til p-hydroxyalkylaminer i henhold til_ den generelle ligning reaction of mono- or diepoxy compounds with di- or polyamines to p-hydroxyalkylamines according to_ the general equation
Denne omsetning er kjent under betegnelsen adduktering. This turnover is known under the term adduction.
Eksempler på brukbare aminer er: Ammoniak, polyethylenpolyaminer,Examples of usable amines are: Ammonia, polyethylene polyamines,
og polypropylenaminer som diethylentriamin og dipropylentriamin, cycloalifatiske.diaminer som l-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexan, også kalt isoforondiamin, 3>3' -dimethyl-h., h 1diamino-dicyclohexyl-methan, heterocycliske aminer som N-amino-ethyl-piperazin, langkjedede polyetheraminer som 1,12-diamino-^,8-di-oxadodecan, aromatiske aminer som fenylendiamin, diamino-difenyl-methan, polyaminoamider, d.v.s. kondensasjonsprodukter av naturlige eller syntetiske hoyere monomere eller dimeriserte fettsyrer med et overskudd av polyaminer. and polypropyleneamines such as diethylenetriamine and dipropylenetriamine, cycloaliphatic diamines such as l-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane, also called isophoronediamine, 3>3'-dimethyl-h., h 1diamino-dicyclohexyl-methane, heterocyclic amines such as N-amino-ethyl-piperazine, long-chain polyetheramines such as 1,12-diamino-^,8-di-oxadodecane, aromatic amines such as phenylenediamine, diamino-diphenyl-methane, polyaminoamides, i.e. condensation products of natural or synthetic higher monomeric or dimerized fatty acids with an excess of polyamines.
Eksempler på en monoepoxyforbindelse er ethylenoksyd, propylenoksyd , styroloksyd eller glycidylethere som butylglycidyl-ether, kresylglycidylether eller glycidylester som glycidylmethacrylat, Som diepoxyforbindelse kan man også bruke glycildylethere av de nevnte difenoler, fortrinnsvis bisfenol-A-diglycidylether, samt glycidylethers av dioller som ethylenglykol, butandiol eller hexandiol og glycildyl-estere av dicarbonsyrer som fthalsyrer, hexahydrofthalsyrer og dimeriserte fettsyrer. Examples of a monoepoxy compound are ethylene oxide, propylene oxide, styrene oxide or glycidyl ethers such as butyl glycidyl ether, cresyl glycidyl ether or glycidyl esters such as glycidyl methacrylate. As a diepoxy compound you can also use glycyldyl ethers of the aforementioned diphenols, preferably bisphenol-A-diglycidyl ether, as well as glycidyl ethers of diols such as ethylene glycol, butanediol or hexanediol and glycyldyl esters of dicarboxylic acids such as phthalic acids, hexahydrophthalic acids and dimerized fatty acids.
Betegnelsen "dimerisert fettsyre" gjelder generelt polymeri-serte syrer som fremstilles av "fettsyrer". Uttrykket "fettsyre" omfatter umettede, naturlige eller syntetiske enbasige alifatiske syrer med 12 til 22 C atomer, fortrinnsvis 18 C atomer. Disse fettsyrer kan polymeriseres på kjent måte (se DT-OS 1 kh^ 938?DT-OS 1 1+1+3 -968, DT-PS 2 118 702 og DT-PS 1 280 852). The term "dimerized fatty acid" generally applies to polymerized acids which are produced from "fatty acids". The term "fatty acid" includes unsaturated, natural or synthetic monobasic aliphatic acids with 12 to 22 C atoms, preferably 18 C atoms. These fatty acids can be polymerized in a known manner (see DT-OS 1 kh^ 938?DT-OS 1 1+1+3 -968, DT-PS 2 118 702 and DT-PS 1 280 852).
Typiske polymere fettsyrer'i handelen har omtrent folgende sammensetning: Typical polymeric fatty acids in the trade have approximately the following composition:
monomere syrer (Mo) 5 - 15 vektprosentmonomeric acids (Mo) 5 - 15 percent by weight
dimere syrer (Di) 60 - 80 vektprosentdimeric acids (Di) 60 - 80 percent by weight
trimere syrer (Tri) 10 - 35 vektprosenttrimer acids (Tri) 10 - 35 percent by weight
Innholdet av dimer syre kan okes ved generelt kjente destillasjonsprosesser inntil loo vektprosent. The content of dimer acid can be increased by generally known distillation processes up to 10% by weight.
Omsetningen til organotinnholdige addukter skjer ved av-s pal ting av HOR-^ , hvor R^ utgjor hydrogen (ved bruk av (R^Sn^O) eller alkyl (ved bruk av R^SnOR1). The conversion to organotin-containing adducts takes place by splitting off HOR-^, where R^ is hydrogen (when using (R^Sn^O)) or alkyl (when using R^SnOR1).
Molforholdet mellom R^Sn-resten og OH-gruppen i det anvendte addukt kan ligge mellom 0,01 : 1 og 1 : 1. Fortrinnsvis velges et molforhold på 0,1 : 1 til 1 : 1. The molar ratio between the R^Sn residue and the OH group in the adduct used can be between 0.01:1 and 1:1. A molar ratio of 0.1:1 to 1:1 is preferably chosen.
Som utgangsforbindelse for organotinnholdige herdere kan man videre benytte kondensasjonsprodukter av fenoler , aldehyder og polyaminer, såkalte rnannichbaser. Condensation products of phenols, aldehydes and polyamines, so-called rnannich bases, can also be used as starting compounds for organotin-containing hardeners.
De anvendbare rnannichbaser kan forenklet beskrives vedThe applicable rnannich bases can be simply described by
hvor symbolene har folgende betydning: where the symbols have the following meaning:
m = 0, 1, 2 m = 0, 1, 2
R^ H, CH3, C2H5, C3H?, ChE9eller C^. R 1 H, CH 3 , C 2 H 5 , C 3 H 2 , ChE 9 or C 2 .
R^ = H, CH3, C(CH3)3, Nonyl. ■ R 3 = H, CH 3 , C(CH 3 ) 3 , Nonyl. ■
R^1 tilsvarer resten av en av de beskrevne polyaminer. R^1 corresponds to the residue of one of the described polyamines.
For fremstilling av organotinnholdige herdere i henhold til oppfinnelsen omsettes mannichbasen med triorganotinnoksyder eller -alkoksyder under avspaltning av HOR^, hvor R^ har den angitte betydning. For the production of organotin-containing hardeners according to the invention, the Mannich base is reacted with triorganotin oxides or -alkoxides while splitting off HOR^, where R^ has the indicated meaning.
Molforholdet mellom R^Sn-resten og den fenoliske OH-gruppe ligger mellom 0,01 : 1 og 1 : 1, fortrinnsvis 0,8 - 1 : 1. The molar ratio between the R^Sn residue and the phenolic OH group is between 0.01:1 and 1:1, preferably 0.8 - 1:1.
Egnede tinnholdige herdere kan videre fremstilles ved å addere di- eller polyamine, henholdsvis polyaminoamider på den aktiverte dobbeltbind ing i a,B-umettede mono- eller dicarbonsyre-trialkyltinnestere: Som aminer kan man bruke de nevnte forbindelser. Eksempler på umettede carbonsyrer hvis trialkyltinnestere kan benyttes er: Acrylsyre samt a- eller |3-alkylsubstituerte acrylsyrer av typen methacrylsyre eller crotonsyre, maleinsyre^itaconsyre, citracon-syre eller alkylidenmalonsyrer med generell formel- Suitable tin-containing hardeners can further be prepared by adding di- or polyamine, respectively polyaminoamides to the activated double bond in a,B-unsaturated mono- or dicarboxylic acid trialkyl tin esters: As amines, the aforementioned compounds can be used. Examples of unsaturated carboxylic acids whose trialkyl tin esters can be used are: Acrylic acid and α- or |3-alkyl substituted acrylic acids of the type methacrylic acid or crotonic acid, maleic acid, itaconic acid, citraconic acid or alkylidenemalonic acids with the general formula
7 8 7 8
hvor R' har betydningen H, CH^ , fenyl og R har betydningen H, CH^ C2H? eller C 1^. where R' has the meaning H, CH^ , phenyl and R has the meaning H, CH^ C2H? or C 1^.
Di- eller polyamine og den umettede trialkyltinnester omsettes i forholdet 1 : 1 eller med underskudd på trialkyltinnester. Di- or polyamine and the unsaturated trialkyl tin ester are reacted in a ratio of 1:1 or with a deficit of trialkyl tin ester.
De organotinnholdige bindemidler i henhold til foreliggende, oppfinnelse har et bredt virkningsspektrum. De er virksomme mot de forskjelligste sopp og bakterier og gir derved de beskyttede underlag som metall, tre, plast o.s.v. en hoy og langvarig beskyttelse. The organotin-containing binders according to the present invention have a broad spectrum of action. They are effective against a wide variety of fungi and bacteria and thereby provide protected substrates such as metal, wood, plastic etc. a high and long-lasting protection.
Innholdet av biocide forbindelser i beleggmassen retter seg etter anvendelsen og kan reguleres på forskjellig måte som f.eks. gjennom The content of biocidal compounds in the coating mass depends on the application and can be regulated in different ways, e.g. through
1) den anvendte epoxyharpikstype og videre ved forholdet1) the type of epoxy resin used and further by the ratio
OH til R^Sn-grupper.OH to R^Sn groups.
2) Den anvendte organotinnholdige aminherder2) The organotin-containing amine hardener used
3) kombinasjonene av3) the combinations of
a) epoxyharpiks i folge oppfinnelsen inneholdene organotinnfri epoxyharpiks, b) epoxyharpiks i folge oppfinnelsen med organotinnfri aminherder, c) organotinnfri epoxyharpiks med aminherder i folge oppfinnelsen. h) Tilsetningen av de vanlige modifiserende midler som fyllstoffer, forsterkningsmidler, akseleratorer, pigmenter a) epoxy resin according to the invention containing organotin-free epoxy resin, b) epoxy resin according to the invention with organotin-free amine hardener, c) organotin-free epoxy resin with amine hardener according to the invention. h) The addition of the usual modifying agents such as fillers, reinforcing agents, accelerators, pigments
o.s.v.etc.
Betydning av forkortelser i folgende eksempler:Meaning of abbreviations in the following examples:
TBTO, = TributyltinnoksydTBTO, = Tributyltin oxide
BPA = Bisfenol-ABPA = Bisphenol-A
EDA = EthylendiaminEDA = Ethylenediamine
AT = AmintallAT = Amine number
THF = TetrahydrofuranTHF = Tetrahydrofuran
EP = EpoxyEP = Epoxy
Fremstillingseksempler på epoxyharpikset og herdere i folge oppfinnelsen. Production examples of the epoxy resin and hardeners according to the invention.
Eksempel 1.Example 1.
En opplosning av 100 g bisfenol-A-epoxyharpiks (epoxy tall 0,21^-, hydroxyltall 0,239), 6)+,3 g (0,108 mol) tributyltinnoksyd og 90 ml toluen kokes ved tilbakelop. I lopet av 5 timer utskiller det seg 1,6 ml.... ( 8h% av teoretisk) vann. Etter avdestillering av toluen blir det tilbake I63 g (99% av teoretisk) hoyviskos harpiks A solution of 100 g bisphenol-A epoxy resin (epoxy number 0.21^-, hydroxyl number 0.239), 6)+.3 g (0.108 mol) tributyltin oxide and 90 ml toluene is refluxed. In the course of 5 hours, 1.6 ml... (8h% of theoretical) water is secreted. After distilling off the toluene, 163 g (99% of theoretical) of high-viscosity resin remains
(Sn-innhold 15,8%).(Sn content 15.8%).
Eksempel 2.Example 2.
100 g glycerolglycidylether (hydroxydtall 0,185) tilsettes 55,3 g (0,093 mol) tributyltinnoksyd i toluenopplosning under aceotrop vannutskilling i 5 timer. Det utskilles 1,5 ml (88% 100 g of glycerol glycidyl ether (hydroxide number 0.185) is added to 55.3 g (0.093 mol) of tributyltin oxide in toluene solution under azeotropic water separation for 5 hours. 1.5 ml (88%
av teoretisk) vann. Man får et lavv.iskost. produkt (Sn-innhold 13,5%), som i folge IR-spekteret ikke inneholder flere 0H-grupper. of theoretical) water. You get a low cost. product (Sn content 13.5%), which, according to the IR spectrum, contains no more OH groups.
Eksempel 3.Example 3.
100 g methylolsubstituert diglycidylether av BPA (epoxytall. 0,38, hydroxyltall 0,17<*>0 tilsettes 51,8 g (0,087 mol) tributyltinnoksyd i toluen i 120 C under aceotrop vannutskilling. Etter 6 timer er det utskilt 1,7 ml (90% av teoretisk). Toluenet avdestilleres. Man får en hoyviskos harpiks (Sn-innhold 13,If%). ' 100 g of methylol-substituted diglycidyl ether of BPA (epoxy number. 0.38, hydroxyl number 0.17<*>0) is added to 51.8 g (0.087 mol) of tributyltin oxide in toluene at 120 C under azeotropic water separation. After 6 hours, 1.7 ml have separated (90% of theoretical). The toluene is distilled off. A highly viscous resin is obtained (Sn content 13.If%).'
Eksempel h .Example h.
Til 32,0 g (0,1 mol) tributyltinnmethoksyd i MeOH tilsettes en.opplosning av 18,0 g (0,1 mol) p-hydroxymethyl-fenylglycidylether 1 100 ml toluen. Etter 1 time ved romtemperatur avdestilleres opplosningsmidlet ved badetemperatur opptil h5° C. Man får ^-3 g krystallinsk produkt (Sn-innhold 25,5%), som i folge IR-spekteret ikke inneholder 0H-bånd lenger. To 32.0 g (0.1 mol) of tributyltin methoxide in MeOH is added a solution of 18.0 g (0.1 mol) of p-hydroxymethyl-phenylglycidyl ether in 1,100 ml of toluene. After 1 hour at room temperature, the solvent is distilled off at a bath temperature of up to h5° C. ^-3 g of crystalline product is obtained (Sn content 25.5%), which, according to the IR spectrum, no longer contains OH bands.
Eksempel 5.Example 5.
En fast epoxyharpiks på bisfenol-A-basis (epoxytall 0,215) omsettes med- et overskudd av ethylendiamin til diglycidylether-ethylendiamin-addukt. 100 g gjenværende addukt etter avdestillering av overskudd EDA (OH-tall 0,<1>+1) oppvarmes med llh g (0,19 mol) tributyltinnoksyd i toluen i 5 timer under aceotrop vannutskilling. Derpå avdestilleres toluen. Man får et viskost produkt med Sn-innhold lik 21, k%. A solid epoxy resin on a bisphenol-A basis (epoxy number 0.215) is reacted with an excess of ethylenediamine to diglycidyl ether-ethylenediamine adduct. 100 g of the remaining adduct after distilling off excess EDA (OH number 0.<1>+1) is heated with llh g (0.19 mol) of tributyltin oxide in toluene for 5 hours under azeotropic water separation. The toluene is then distilled off. A viscous product with a Sn content equal to 21.k% is obtained.
Eksempel 6.Example 6.
50 g 1 : 1 -addukt av diethylentriamin og propylenoksyd (0H-tall 0,62) omsettes med 92,5 g (0,155 mol) tributyltinnoksyd i toluen under aceotrop vannutskilling. Etter 6 timer er det utskilt 2,!+ ml vann (86% av teoretisk). Etter avdestillering av opplosningsmidlet får man et lavviskost produkt (Sn-innhold lik 25,9%) som i folge IR-spekteret ikke lenger inneholder 0H-grupper. 50 g of a 1:1 adduct of diethylenetriamine and propylene oxide (OH number 0.62) is reacted with 92.5 g (0.155 mol) of tributyltin oxide in toluene under azeotropic separation of water. After 6 hours, 2.!+ ml of water has been secreted (86% of theoretical). After distilling off the solvent, a low-viscosity product is obtained (Sn content equal to 25.9%) which, according to the IR spectrum, no longer contains OH groups.
Eksempel 7.Example 7.
Fenol, formaldehyd og trimethyl-hexamethylendiamin omsettes i mol forholdet 1:1:1 til en mannichbase med hydroxyltall 0,376. 130 g av denne basen omsettes med 138 g (0,232 mol) TBT0 Phenol, formaldehyde and trimethyl-hexamethylenediamine are converted in a molar ratio of 1:1:1 to a Mannich base with a hydroxyl number of 0.376. 130 g of this base is reacted with 138 g (0.232 mol) TBT0
i 80 g toluen under aceotrop vannutskilling. Det dannede produkt (Sn-innhold lik 20,8%) er i folge IR-spekteret fri for 0H-grupper. in 80 g of toluene under azeotropic water separation. The product formed (Sn content equal to 20.8%) is, according to the IR spectrum, free of OH groups.
Eksempel 8.Example 8.
Hydrochinon, formaldehyd og diethylentriamin omsettes i molforhold 1:1:1 til en mannichbase med et amintall lik 738 Hydroquinone, formaldehyde and diethylenetriamine are reacted in a molar ratio of 1:1:1 to a Mannich base with an amine number equal to 738
og et fenoltall lik 1+50. 100 g (0H-tall 0,*f) av mannichbasen omsettes med 120 g (0,2 mol) TBT0 i 80 g toluen under aceotrop vannutskilling. Etter 5 timer er det dannet 3 A ml vann ( 9h% and a phenol number equal to 1+50. 100 g (OH number 0.*f) of the Mannich base is reacted with 120 g (0.2 mol) TBT0 in 80 g toluene under azeotropic water separation. After 5 hours, 3 A ml of water has been formed (9h%
av teoretisk). Etter avdestillering av toluenet får man et produkt med Sn-innhold lik 21,8%. of theoretical). After distilling off the toluene, a product with a Sn content equal to 21.8% is obtained.
Eksempel 9.Example 9.
131,6 g hexahydrofthalsyrediglycidylester (epoxy-tall 0,5*+) omsettes med 38,*+ g bisfenol-A i nærvær av 0,07 g anhydro-succinyliden-trifenyl-fosforan ved 120° C til et produkt med epoxytall lik 0,19 (teoretisk 0,22) og et OH-tall på 202. 50,Og 131.6 g of hexahydrophthalic acid glycidyl ester (epoxy number 0.5*+) is reacted with 38.*+ g bisphenol-A in the presence of 0.07 g of anhydro-succinylidene-triphenyl-phosphorane at 120° C to a product with an epoxy number equal to 0 ,19 (theoretical 0.22) and an OH number of 202. 50,And
.omsettes med 53?9g (0,093 mol) tributyltinnoksyd i nærvær av.is reacted with 53.9g (0.093 mol) tributyltin oxide in the presence of
50 g toluen i k timer under tilbakelopskoking. Det utskilles 1,3 ml vann (81,3% av teoretisk). Det dannede produktet er i folge infrarodt spektrum fri for 0H-grupper. 50 g toluene for k hours under reflux. 1.3 ml of water is secreted (81.3% of theoretical). According to the infrared spectrum, the product formed is free of 0H groups.
Eksempel 10.Example 10.
109 g (1,0 mol) o-aminofenol og 298 g (0,5 mol) tributyltinnoksyd oppvarmes i toluen i 2 timer under aceotrop vannutskilling. Det utskilles 8, 3 ml (95% av teoretisk) vann. Etter avdestillering av opplosningsmidlet får man et produkt (Sn-innhold lik 29,<*>+%) som er uten OH-grupper. 109 g (1.0 mol) of o-aminophenol and 298 g (0.5 mol) of tributyltin oxide are heated in toluene for 2 hours under azeotropic separation of water. 8.3 ml (95% of theoretical) water is secreted. After distilling off the solvent, a product is obtained (Sn content equal to 29.<*>+%) which is without OH groups.
Eksempel 11.Example 11.
7o,8 g (0,1 mol) itaconsyre-di(tributyltinnester) oppvarmes med 19,0 g (0,12 mol) trimethylexamethyleridiamin i THF ved romtemperatur. Etter 20 timer avdestilleres opplosningsmidlet og overskuddet av amin destilleres i vakuum. Man får et seigt .gult produkt med AT 115 og Sn-innhold 26,6%. 70.8 g (0.1 mol) of itaconic acid di(tributyltin ester) is heated with 19.0 g (0.12 mol) of trimethylhexamethyleridiamine in THF at room temperature. After 20 hours, the solvent is distilled off and the excess of amine is distilled off in a vacuum. You get a tough, yellow product with AT 115 and a Sn content of 26.6%.
Eksempel 12.Example 12.
72,2 g (0,2 mol) tributyltinnacrylat i THF dryppes i lopet av 2 timer til en opplosning av 15,0 g (0,25 mol) ethylendiamin i THF. Det inntrer en exotherm reaksjon. Etter avsluttet tilsetning rores i 20 timer ved romtemperatur. Deretter destilleres opplosningsmidlet og aminoverskuddet fra. Det dannede produktet har et amintall lik 2>+8, Sn-innhold lik 27,7%. 72.2 g (0.2 mol) of tributyltin acrylate in THF are added dropwise over the course of 2 hours to a solution of 15.0 g (0.25 mol) of ethylenediamine in THF. An exothermic reaction occurs. After the addition is complete, stir for 20 hours at room temperature. The solvent and the excess amine are then distilled off. The product formed has an amine number equal to 2>+8, Sn content equal to 27.7%.
Eksempel 13.Example 13.
72,2 g' (0,2 mol) tribultyltinnacrylat opploses i THF, tilsettes i lopet av 2 timer til 31,6 g (0,2 mol) trimethylhexamethylendiamin. Man rorer i 20 timer ved romtemperatur og avdestillerer THF ved normaltrykk og uomsatt amin (0,<*>+ g) ved oljepumpevacuum. 72.2 g' (0.2 mol) of tributyl tin acrylate are dissolved in THF, added over the course of 2 hours to 31.6 g (0.2 mol) of trimethylhexamethylenediamine. Stir for 20 hours at room temperature and distill off THF at normal pressure and unreacted amine (0.<*>+ g) at oil pump vacuum.
Man får et produkt med AT lik 250, Sn-innhold 20,8%.You get a product with AT equal to 250, Sn content 20.8%.
Fremstillinger av malinger.Production of paints.
De organotinnholdige glycidylforbindelser eller herdere i folge oppfinnelsen, ble for å oppnå bedre sammenligningsgrunnlag, innstilt på et -tinninnhold lik 1% ved tilsetning av organotinnfrie glycidylforbindelser eller herdere, den angitte prosent regnet på basis av beleggets torrvekt. The organotin-containing glycidyl compounds or hardeners according to the invention, in order to obtain a better basis for comparison, were set to a tin content equal to 1% by adding organotin-free glycidyl compounds or hardeners, the specified percentage calculated on the basis of the dry weight of the coating.
Eksempel 1^-.Example 1^-.
h-, 7 g adduktherder i folge eksempel 5 blandes med 90,9 g 75%ig xylen-opplosning av fast epoxyharpiks på bisfenol A-basis (epoxy-tall 0,215) samt ^-9,3 g 55%ig opplosning isolert ethylendiamin-bisfenol-A-epoxyharpiks-addukt (amintall 210). Et papir-f ilter med diameter 55 mm ble bestroket med 0 ,>+ g av denne blanding. h-, 7 g of adduct hardener according to example 5 is mixed with 90.9 g of a 75% xylene solution of solid epoxy resin on a bisphenol A basis (epoxy number 0.215) and ^-9.3 g of a 55% solution of isolated ethylenediamine bisphenol-A epoxy resin adduct (amine number 210). A paper filter with a diameter of 55 mm was coated with 0.5 g of this mixture.
Eksempel 15.Example 15.
2,3 g av en forbindelse i folge eksempel 12 ble tilsatt 78,8 g 75%ig xylen-opplosnlng av en fast epoxyharpiks på bisfenol-A-basis (Ep-tall = 0,215) og'1,6 g ethylendiamin ble blandet inn hvorpå malinge ble stroket ut på filtrerpapir som under eksempel 1<*>+. 2.3 g of a compound according to example 12 was added to 78.8 g of a 75% xylene solution of a solid epoxy resin on a bisphenol-A basis (Ep number = 0.215) and 1.6 g of ethylenediamine was mixed in after which paint was stroked out on filter paper as under example 1<*>+.
Eksempel 16.Example 16.
8,3 g epoxyforbindelse i folge eksempel 1 og 69,6 g 75%ig opplosning av fast epoxy.harp.Lks ble som i eksempel 15 blandet med ^358 g 55%ig opplosning av isolert ethylendiamin-epoxyharpiks- 8.3 g of epoxy compound according to example 1 and 69.6 g of a 75% solution of solid epoxy.harp.Lks were mixed as in example 15 with ^358 g of a 55% solution of isolated ethylenediamine-epoxy resin-
addukt (amintall 210) og et papirfilter bestroket som i eksempel lh. adduct (amine number 210) and a paper filter coated as in example lh.
Eksempel 17.Example 17.
'3 58 g forbindelse i folge eksempel. 11 ble blandet med 120 g 75%ig opplosning av fast epoxyharpiks i folge eksempel 15?og blandet med 6,5 g trimethylhexamethylendiamin hvorpå et papirfilter ble bestroket som i eksempel l^. '3 58 g of compound according to example. 11 was mixed with 120 g of a 75% solution of solid epoxy resin according to example 15? and mixed with 6.5 g of trimethylhexamethylenediamine, on which a paper filter was coated as in example 1^.
Eksempel 18.Example 18.
2,2 g av forbindelsen i folge krav 7 ble blandet med 2,9 g mannichbase av trimethylhexamethylendiamin,formaldehyd og fenol i forholdet 1 : 1 : 1 og ^+3,9 75%ig opplosning av fast epoxyharpiks som i eksempel 155og et papirfilter bestroket i folge eksempel 1^. 2.2 g of the compound according to claim 7 was mixed with 2.9 g of Mannich base of trimethylhexamethylenediamine, formaldehyde and phenol in the ratio 1 : 1 : 1 and ^+3.9 75% solution of solid epoxy resin as in example 155 and a paper filter coated according to example 1^.
Sammenligningseksempel.Comparative example.
20 g 75%ig xylé-n-opplosning av epoxyharpiks i folge eksempel20 g of 75% xylé-n solution of epoxy resin according to the example
15 og 12 g 55%ig opplosning av isolert ethylendiamin-epoxyharpiks-addukt (AT 210) ble blandet. Man bestrok et papirfilter som i eksempel Ih- med denne blanding. 15 and 12 g of a 55% solution of isolated ethylenediamine epoxy resin adduct (AT 210) were mixed. A paper filter as in example Ih- was coated with this mixture.
UndersokeIse av den biocide virkning.Examination of the biocidal effect.
For å gjennomfore biocidforsokene ble næringsagar helt opp i petriskåler med diameter 10 cm. Etter at agaren var stivnet ble papirfUtrene lagt på og pådusjet oppslemminger av forsoksbakterier og -sopp. To carry out the biocide experiments, nutrient agar was poured into Petri dishes with a diameter of 10 cm. After the agar had solidified, the paper tubes were placed on and sprinkled with slurries of prebiotic bacteria and fungi.
Konsentrasjonen av forsoksbakteri er og -sopp ble fotometrisk provet i 1 cm tykk kyvette. The concentration of presox bacteria and fungi was photometrically tested in a 1 cm thick cuvette.
Oppslemmingens ekstinksjonstall ble målt i spektralfotometerets Zeiss PMQ 2. Ved<1>+20yu.fikk man mot vann som referanse folgende ekstinksjonstall: The extinction figure of the slurry was measured in the Zeiss PMQ 2 spectrophotometer. At <1>+20yu., the following extinction figure was obtained against water as a reference:
Deretter lot man soppene, vokse i 3 uker ved 30° C og bakteriene h dager ved 37<0>C. The fungi were then allowed to grow for 3 weeks at 30°C and the bacteria for 37 days at 37<0>C.
Bedømmelsen av den biocide virkning ble foretatt 1.henhold til begrolngens styrke og inhiberlngssoneries størrelse omkring forsoks-skivene. The assessment of the biocidal effect was carried out 1. according to the strength of the fouling and the size of the zone of inhibition around the test disks.
Undersøkelse av den begronlngshindrende virkning. Examination of the anti-fouling effect.
Sandblåste og grunningsmalte stålblikk med mål 15 x 10 cm ble to ganger på begge sider belagt med forsoksmalinger som var pigmentert med rutil i vektforholdet 1 : 1 på torrbasis. Harpiks og herdere ble opplost i vanlige opplosningsmidler for disse komponenter og innstilt på et faststoffinnhold, som sikret en glatt bearbeidelse og blandet i stochiometrisk forhold. Sandblasted and primer-painted steel sheets measuring 15 x 10 cm were coated twice on both sides with trial paints that were pigmented with rutile in a weight ratio of 1:1 on a dry basis. Resins and hardeners were dissolved in common solvents for these components and adjusted to a solids content that ensured smooth processing and mixed in a stoichiometric ratio.
Etter torking ble forsoksplatene provet i en sjovann-forsoksstasjon i Cuxhaven med hensyn på begroing med sjovanns-organismer. After drying, the trial plates were tested in a fresh water test station in Cuxhaven with regard to fouling with fresh water organisms.
Eksempel 19.Example 19.
Tinnholdige herdere i folge eksempel 5 omsatt med fast epoxyharpiks på BPA-basis (Ep-tall = 0,215), tinninnhold = 5,1% Tin-containing hardeners according to example 5 reacted with solid epoxy resin on a BPA basis (Ep number = 0.215), tin content = 5.1%
i torrfilmen.in the dry film.
Eksempel 20.Example 20.
Tinnholdige epoxyharpiks i folge eksempel 1, omsatt med et isolert ethylendiamin-epoxyharpiks-addukt (fast Ep-harpiks på BPA-basis, Ep-tall = 0,215), tinninnhold i torrfilmen = 6,3%. Tin-containing epoxy resins according to example 1, reacted with an isolated ethylenediamine-epoxy resin adduct (solid Ep resin on a BPA basis, Ep number = 0.215), tin content in the dry film = 6.3%.
Eksempel 21.Example 21.
Tinnholdige epoxyharpiks i folge eksempel 1, omsatt med tinnholdige herdere i folge eksempel 5, torrfilmens torrinnhold = 8,9%. Tin-containing epoxy resins according to example 1, reacted with tin-containing hardeners according to example 5, dry film dry content = 8.9%.
Eksempel 22.Example 22.
Tinnholdig herder i folge eksempel 7, omsatt med tinn-hold ig epoxyharpiks i folge eksempel 1, torrfilmens tinninnhold = 8,1$. Tin-containing hardener according to example 7, reacted with tin-containing epoxy resin according to example 1, tin content of the dry film = 8.1$.
Eksempel 23.Example 23.
Tinnholdig herder i folge eksempel 5, omsatt med en blanding av diglycidylester av dimerisert talloljefettsyre (Ep-tall - 0,25) og flytende bisfenol-A-epoxyharpiks (Ep-tall = Q,53) i vektforhold 1/1, tinninnhold for torrfilmen = 6,7%. Tin-containing hardener according to example 5, reacted with a mixture of diglycidyl ester of dimerized tall oil fatty acid (Ep number - 0.25) and liquid bisphenol-A epoxy resin (Ep number = Q.53) in a weight ratio of 1/1, tin content for the dry film = 6.7%.
Sammenligningseksempel.Comparative example.
Fast bisfenol-A-epoxyharpiks (Ep-tall = 0,215) omsatt med isolert ethylendiamin-addukt av samme epoxyharpiks med et amintall likt 210. Solid bisphenol-A epoxy resin (Ep number = 0.215) reacted with isolated ethylenediamine adduct of the same epoxy resin with an amine number equal to 210.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19762647604 DE2647604A1 (en) | 1976-10-21 | 1976-10-21 | Biocidal coatings contg. organo-tin gps. - covalently bonded to epoxy! and hardener components, esp. for slow release marine antifouling paints |
DE19762647605 DE2647605A1 (en) | 1976-10-21 | 1976-10-21 | Biocidal coatings contg. organo-tin gps. - covalently bonded to epoxy! and hardener components, esp. for slow release marine antifouling paints |
Publications (1)
Publication Number | Publication Date |
---|---|
NO773601L true NO773601L (en) | 1978-04-24 |
Family
ID=25771040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO773601A NO773601L (en) | 1976-10-21 | 1977-10-20 | ARTIC RESIN COMPONENTS FOR THE MANUFACTURE OF BIOCIDE COATINGS |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS5351236A (en) |
DK (1) | DK426277A (en) |
ES (1) | ES462158A1 (en) |
FR (1) | FR2368522A1 (en) |
IT (1) | IT1086150B (en) |
LU (1) | LU78348A1 (en) |
NL (1) | NL7710810A (en) |
NO (1) | NO773601L (en) |
SE (1) | SE7711818L (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS59142264A (en) * | 1983-02-02 | 1984-08-15 | Nitto Electric Ind Co Ltd | Film-forming coating composition containing liquid active substance |
JPS59169879U (en) * | 1983-04-28 | 1984-11-13 | 株式会社学習研究社 | stationery robot |
-
1977
- 1977-09-06 ES ES462158A patent/ES462158A1/en not_active Expired
- 1977-09-27 DK DK426277A patent/DK426277A/en not_active Application Discontinuation
- 1977-09-28 IT IT28012/77A patent/IT1086150B/en active
- 1977-10-03 NL NL7710810A patent/NL7710810A/en not_active Application Discontinuation
- 1977-10-19 LU LU78348A patent/LU78348A1/xx unknown
- 1977-10-20 SE SE7711818A patent/SE7711818L/en unknown
- 1977-10-20 NO NO773601A patent/NO773601L/en unknown
- 1977-10-20 JP JP12637177A patent/JPS5351236A/en active Pending
- 1977-10-20 FR FR7731576A patent/FR2368522A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
SE7711818L (en) | 1978-04-22 |
DK426277A (en) | 1978-04-22 |
ES462158A1 (en) | 1979-01-01 |
IT1086150B (en) | 1985-05-28 |
JPS5351236A (en) | 1978-05-10 |
FR2368522A1 (en) | 1978-05-19 |
LU78348A1 (en) | 1978-01-24 |
NL7710810A (en) | 1978-04-25 |
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