NO162666B - PROCEDURE FOR THE MANUFACTURING OF RESPECTABLE MATERIALS. - Google Patents
PROCEDURE FOR THE MANUFACTURING OF RESPECTABLE MATERIALS. Download PDFInfo
- Publication number
- NO162666B NO162666B NO851109A NO851109A NO162666B NO 162666 B NO162666 B NO 162666B NO 851109 A NO851109 A NO 851109A NO 851109 A NO851109 A NO 851109A NO 162666 B NO162666 B NO 162666B
- Authority
- NO
- Norway
- Prior art keywords
- group
- acid
- resin
- atoms
- phenol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 title description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 127
- 239000000203 mixture Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 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 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- -1 azo compound Chemical class 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229930185605 Bisphenol Natural products 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 239000012262 resinous product Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 235000003704 aspartic acid Nutrition 0.000 claims description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 6
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 108010077895 Sarcosine Proteins 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229940043230 sarcosine Drugs 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 229960005261 aspartic acid Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000003505 polymerization initiator Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 50
- 239000000243 solution Substances 0.000 description 33
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 20
- 239000003999 initiator Substances 0.000 description 20
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- 229930040373 Paraformaldehyde Natural products 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920002866 paraformaldehyde Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 9
- 239000004342 Benzoyl peroxide Substances 0.000 description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 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 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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Classifications
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/38—Block or graft polymers prepared by polycondensation of aldehydes or ketones onto macromolecular compounds
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av harpiksholdige materialer som kan fortynnes med vann. The present invention relates to a method for the production of resinous materials which can be diluted with water.
For å oppnå et kqrrosjonsresistent belegg på metallbeholdere er det vanlig å belegge metalloverflaten med en tverrbindbar harpikssammensetning oppløst i et organisk oppløsningsmiddel, og deretter oppvarme belegget for å fordampe oppløsnings-midlet og tverrbinde harpiksen. Tverrbinding av belegget omvandler det til en sterk, vedhengende, fleksibel og beskyttende film. Under oppvarmingen fordampes oppløsnings-midlet vanligvis til atmosfæren. Siden organiske oppløsnings-midler er relativt dyre, lett antennelige og vanligvis miljøskadelige, eksisterer dét et behov for belegg som kan påføres ved bruk av minimale mengder slike oppløsningsmidler, spesielt nyttige er beleggsammensetninger som inneholder en stor andel vann. In order to achieve a corrosion-resistant coating on metal containers, it is common to coat the metal surface with a crosslinkable resin composition dissolved in an organic solvent, and then heat the coating to evaporate the solvent and crosslink the resin. Cross-linking of the coating transforms it into a strong, adherent, flexible and protective film. During the heating, the solvent is usually evaporated to the atmosphere. Since organic solvents are relatively expensive, easily flammable and usually harmful to the environment, there is a need for coatings that can be applied using minimal amounts of such solvents, particularly useful are coating compositions that contain a large proportion of water.
T US-patent nr. 4,362,853 beskrives harpikssalter fremstilt fra en fenol-terminert harpiks ved en Mannich-reaksjon med en aminosyre og et aldehyd, med fullstendig eller delvis nøytralisering av karboksylsyregruppen eller gruppene innført ved aminosyren. US Patent No. 4,362,853 describes resin salts prepared from a phenol-terminated resin by a Mannich reaction with an amino acid and an aldehyde, with complete or partial neutralization of the carboxylic acid group or groups introduced at the amino acid.
I vest-tysk utlegningsskrift nr. 3,247,281 beskrives harpikssaltet fremstilt fra en fenol-terminert harpiks, enten ved tioalkylering med en merkåptokarboksylsyre og et aldehyd etterfulgt av en i det minste delvis nøytral-isering av karboksylsyregruppen(e) innført ved merkapto-karboksylsyren, eller ved sulfoalkylering ■ med svovelsyre (eller et vann-oppløselig salt derav) og et aldehyd, om nødvendig etterfulgt av i det minste delvis nøytralisering av sulfonsyregruppen(e) innført ved svovelsyren eller dens salt. In West German Explanatory Document No. 3,247,281, the resin salt prepared from a phenol-terminated resin is described, either by thioalkylation with a mercaptocarboxylic acid and an aldehyde followed by at least partial neutralization of the carboxylic acid group(s) introduced by the mercaptocarboxylic acid, or by sulfoalkylation ■ with sulfuric acid (or a water-soluble salt thereof) and an aldehyde, if necessary followed by at least partial neutralization of the sulfonic acid group(s) introduced by the sulfuric acid or its salt.
Andre harpikssalter er beskrevet i britisk patent nr. 2,118,936 A. Disse saltene fremstilles fra en fenol-terminert harpiks ved en Mannich-reaksjon med et aldehyd eller en aminofosfonsyre eller en aminosulfonsyre etterfulgt ved fullstendig, eller delvis, nøytralisering av syregruppen(é) innført ved denne reaksjonen. Other resin salts are described in British Patent No. 2,118,936 A. These salts are prepared from a phenol-terminated resin by a Mannich reaction with an aldehyde or an aminophosphonic acid or an aminosulfonic acid followed by complete or partial neutralization of the acid group(é) introduced by this reaction.
Hvert av de ovenfor nevnte patenter beskriver anvendelsen av harpikssalter, enten alene eller sammen med en aminoplast, en fenoplast eller et blokkdannet polyisocyanat, i vandige sammensetninger for overflatebelegg. Each of the above-mentioned patents describes the use of resin salts, either alone or together with an aminoplast, a phenoplast or a block-formed polyisocyanate, in aqueous compositions for surface coatings.
I US-patent nr. 4,308,185 beskrives en fremgangsmåte hvor en epoksyharpiks omsettes med en addisjonspolymeriserbar monomer slik at det dannes en podet polymer. Por fremstilling av et vann-dispergerbart produkt benyttes en karboksyl-funksjonell monomer; for å begrense reaksjonen av epoksygruppene i harpiksen med karboksylgruppene i monomeren omsettes harpiksen med et termineringsmiddel, som kan være bisfenol A, for å fjerne noen av, eller alle, epoksygruppene. US patent no. 4,308,185 describes a method where an epoxy resin is reacted with an addition polymerizable monomer so that a grafted polymer is formed. For the production of a water-dispersible product, a carboxyl-functional monomer is used; in order to limit the reaction of the epoxy groups in the resin with the carboxyl groups in the monomer, the resin is reacted with a terminating agent, which may be bisphenol A, to remove some or all of the epoxy groups.
Det er nå funnet at egenskapene for harpiksholdige reak-sjonsprodukter av en fenol-terminert harpiks, et aldehyd og en syre (eller salt), som de som er beskrevet ovenfor, kan forbedres ved en modifisering som innbefatter polymerisering av en vinylmonomer i den fenol-terminerte harpiksen, eller et forstadium av denne, før reaksjonen med aldehydet og syren (eller saltet). Spesielt kan vandige beleggsammensetninger som har en høyere viskositet for et gitt faststoffinnhold oppnås dersom de modifiserte produktene innbefattes, og belegg som har forbedret syre-resistens kan oppnås. Det finnes i de ovenfor nevnte patentskriftene ingen antydning om at en slik modifisering ville gi et fordelaktig resultat. It has now been found that the properties of resinous reaction products of a phenol-terminated resin, an aldehyde and an acid (or salt), such as those described above, can be improved by a modification involving polymerization of a vinyl monomer in the phenolic terminated the resin, or a precursor thereof, prior to reaction with the aldehyde and the acid (or salt). In particular, aqueous coating compositions having a higher viscosity for a given solids content can be obtained if the modified products are included, and coatings having improved acid resistance can be obtained. There is no indication in the above-mentioned patent documents that such a modification would produce an advantageous result.
Følgelig tilveiebringer foreliggende oppfinnelse en fremgangsmåte for fremstilling av harpiksmaterialer som kan fortynnes med vann som innbefatter at følgende komponenter omsettes: (A) en harpiks som har minst en fenolisk hydroksylgruppe og en fri posisjon i orto— og/eller paraposisjon til Accordingly, the present invention provides a process for the production of resin materials that can be diluted with water which includes reacting the following components: (A) a resin having at least one phenolic hydroxyl group and a free position in the ortho and/or para position to
den fenoliske hydroksylgruppen, med the phenolic hydroxyl group, med
(B) et aldehyd, og (B) an aldehyde, and
(C) en svovelsyre eller en organisk syre som inneholder (C) a sulfuric acid or an organic acid containing
en primær eller sekundær aminogruppe eller en a primary or secondary amino group or a
merkaptangruppe og en karboksylsyre—, sulfonsyre— eller fosfonsyregruppe, eller et vannoppløselig salt derav. mercaptan group and a carboxylic acid, sulphonic acid or phosphonic acid group, or a water-soluble salt thereof.
Fremgangsmåten er kjennetegnet ved at harpiksen (A) inneholder en rest dannet ved polymerisasjon av en vihylmonomer i harpiksen, eller et forstadium av denne. The method is characterized by the fact that the resin (A) contains a residue formed by polymerization of a vihyl monomer in the resin, or a precursor thereof.
Harpiksen (A) har generelt fra 1 til 4 fenoliske hydroksylgrupper, harpikser som gjennomsnittlig har mellom 1 og 2 fenoliske hydroksylgrupper pr. molekyl foretrekkes. Fortrinnsvis har harpiksen en ryggrad avledet fra en epoksyharpiks eller fenoksyharpiks. Molekylvekten av harpiksen er vanligvis fra 1 000 til 10 000, fortrinnsvis fra 2 000 til 4 000. The resin (A) generally has from 1 to 4 phenolic hydroxyl groups, resins which on average have between 1 and 2 phenolic hydroxyl groups per molecule is preferred. Preferably, the resin has a backbone derived from an epoxy resin or phenoxy resin. The molecular weight of the resin is usually from 1,000 to 10,000, preferably from 2,000 to 4,000.
Egnede harpikser (A) er de som oppnås ved å omsette en epoksyharpiks med en flerverdig fenol som har en fri posisjon orto og/eller para til en fenolisk hydroksylgruppe, slik at det dannes en fenol-terminert harpiks og deretter polymeri-sere en vinylmonomer i den sistnevnte. Kjente fremgangsmåter kan benyttes for å omsette epoksyharpiksen med den flerverdige fenolen. Fortrinnsvis er epoksyharpiksen et diepoksyd og den flerverdige fenolen er en toverdig fenol; det må være minst like mye toverdig fenol tilstede, på molar basis, som det finnes diepoksyd, for å gi et produkt som har minst en terminal fenolisk hydroksylgruppe. Det molare forholdet mellom diepoksyd og toverdig fenol ligger vanligvis innen området 1:1,02 til 1:1,6, spesielt 1:1,1 til 1:1,5. Den foretrukne fremgangsmåten for gjennomføring av reaksjonen er å oppvarme reaktantene til 100-200°C i nærvær av en base, som kan være et tertiært amin, men som fortrinnsvis er et alkalimetall-hydroksyd. Reaksjonen kan utføres i et inert oppløsnings-middel. Suitable resins (A) are those obtained by reacting an epoxy resin with a polyhydric phenol having a free position ortho and/or para to a phenolic hydroxyl group, so that a phenol-terminated resin is formed and then polymerizing a vinyl monomer in the latter. Known methods can be used to react the epoxy resin with the polyhydric phenol. Preferably, the epoxy resin is a diepoxide and the polyhydric phenol is a dihydric phenol; there must be at least as much divalent phenol present, on a molar basis, as there is diepoxide to give a product having at least one terminal phenolic hydroxyl group. The molar ratio of diepoxide to dihydric phenol is usually in the range of 1:1.02 to 1:1.6, especially 1:1.1 to 1:1.5. The preferred method for carrying out the reaction is to heat the reactants to 100-200°C in the presence of a base, which may be a tertiary amine, but which is preferably an alkali metal hydroxide. The reaction can be carried out in an inert solvent.
Den toverdige fenolen som benyttes i reaksjonen med epoksyharpiksen kan være en mononukleær fenol som f.eks. hydrokinon eller resorsinol men er fortrinnsvis en bisfenol, som kan være substituert, spesielt en forbindelse av formelen: The divalent phenol used in the reaction with the epoxy resin can be a mononuclear phenol such as e.g. hydroquinone or resorcinol but is preferably a bisphenol, which may be substituted, especially a compound of the formula:
hvor hver R<1>, som kan være de samme eller forskjellige, står for et hydrogenatom, et halogenatom, en alkylgruppe på 1 til 4 karbonatomer, eller en alkenylgruppe på 2 til 4 karbonatomer, under den forutsetning at minst 1 av R<1 >gruppene orto til en fenolisk hydroksylgruppe er et hydrogenatom, og where each R<1>, which may be the same or different, represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, provided that at least 1 of R<1 >the groups ortho to a phenolic hydroxyl group are a hydrogen atom, and
X står for en alkylen- eller alkylidengruppe på 1 til 3 karbonatomer, en karbonyl- eller sulfonylgruppe, et oksygen- eller svovelatom, eller en valensbinding. X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond.
Eksempler på spesielt foretrukne bisfenoler er bis(4-hydroksyfenyl)metan og 2,2-bis(4-hydroksyfenyl)propan. Epoksyharpikser (polyepoksyder) som er foretrukket for omsetning med den toverdige fenolen er de som inneholder to terminale gly idylgrupper direkte forbundet med et atom, eller atomer, av oksygen, nitrogen, eller svovel. Examples of particularly preferred bisphenols are bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane. Epoxy resins (polyepoxides) which are preferred for reaction with the divalent phenol are those which contain two terminal glycidyl groups directly linked to an atom, or atoms, of oxygen, nitrogen, or sulfur.
Som eksempler på slike harpikser kan nevnes polyglycidylestere som kan oppnås ved reaksjon mellom en forbindelsa som inneholder 2 karboksylsyregrupper pr. molekyl og epiklorhydrin eller glyseroldiklorhydrin i nærvær av alkali. Slike polyglycidylestere kan avledes fra alifatiske polykarboksylsyrer, f.eks. oksalsyre, ravsyre, glutarsyre, adipinsyre, pimelinsyre, suberinsyre, azelain-syre, sebasinsyre, og dimerisert linolsyre; fra cykloalifatiske polykarboksylsyrer som f.eks. tetrahydroftalsyre, 4-metyltetrahydroftalsyre, heksahydroftalsyre, og 4-metyl-heksahydroftalsyre; og fra aromatiske polykarboksylsyrer, som f.eks. ftalsyre, isoftalsyre, og tereftalsyre. Examples of such resins include polyglycidyl esters which can be obtained by reaction between a compound containing 2 carboxylic acid groups per molecule and epichlorohydrin or glycerol dichlorohydrin in the presence of alkali. Such polyglycidyl esters can be derived from aliphatic polycarboxylic acids, e.g. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimerized linoleic acid; from cycloaliphatic polycarboxylic acids such as e.g. tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methyl-hexahydrophthalic acid; and from aromatic polycarboxylic acids, such as e.g. phthalic acid, isophthalic acid, and terephthalic acid.
Ytterligere eksempler er polyglycidyletere som kan oppnås ved reaksjon mellom en forbindelse som inneholder minst to frie alkolholiske hydroksyl- eller fenoliske hydroksylgrupper pr. molekyl og epiklorhydrin eller glyseroldiklorhydrin under alkaliske betingelser, eller alternativt i nærvær av en syrekatalysator med etterfølgende behandling med alkali. Disse eterene kan fremstilles fra acykl.iske alkoholer som f.eks. etylenglykol, dietylenglykol, og høyere poly(oksyetylen) glykoler, propan-1,2-diol og poly(oksypropylen) glykoler, propan-1,3-diol, butan-1,4-diol, poly(oksytetrametylen) glykoler, pentan-1,5-diol, og polyepiklorhydriner fra cykloalifatiske alkoholer som f.eks. resorsitol, kinintol, bis(4-hydroksycykloheksyl)-metan, 2,2-bis(4-hydroksycykloheksyl)propan, og 1,1-bis(hydroksymetyl)cykloheks-3-ene; og fra alkoholer som har aromatisk kjerne, som f.eks. N,N-bis(2-hydroksyetyl)-anilin og p,p'-bis(2-hydroksyetylamino)difenylmetan. Eller de kan fremstilles fra mononukleære fenoler, som f.eks. resorsinol og hydrokinon, og fra polynukleære fenoler, som f.eks. bis(4-hydroksyfenyl)metan, 4,4'-dihydroksydifenyl, bis(4-hydroksyfenyl) sulfon, 2,2-bis(4-hydroksyfenyl)propan, 2,2-bis(3,5-dibromo-4-hydroksy-fenyl)propan. og 2, 2-bis(2-allyl-4-hydroksyfenyl)propan. Further examples are polyglycidyl ethers which can be obtained by reaction between a compound containing at least two free alcoholic hydroxyl or phenolic hydroxyl groups per molecule and epichlorohydrin or glycerol dichlorohydrin under alkaline conditions, or alternatively in the presence of an acid catalyst with subsequent treatment with alkali. These ethers can be prepared from acyclic alcohols such as e.g. ethylene glycol, diethylene glycol, and higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane- 1,5-diol, and polyepichlorohydrins from cycloaliphatic alcohols such as e.g. resorsitol, quinintole, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and 1,1-bis(hydroxymethyl)cyclohex-3-ene; and from alcohols that have an aromatic core, such as e.g. N,N-bis(2-hydroxyethyl)-aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. Or they can be prepared from mononuclear phenols, such as e.g. resorcinol and hydroquinone, and from polynuclear phenols, such as e.g. bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl) sulfone, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxy -phenyl)propane. and 2,2-bis(2-allyl-4-hydroxyphenyl)propane.
Poly(N-glycidyl) forbindelser innbefatter, f.eks., de som dannes ved' hydroklorerinq av reaksjonsproduktene mellom epiklorhydrin og aminer som inneholder to amino-hydrogenatomer som f.eks. anilin, n-butylamin, og bis(4-metylaminofenyl)metan; og N,N'-diglysidyl derivater av cykliske alkylenureaforbindelser, som f.eks. etylenurea og 1,3-propylenurea, og av hydantoiner som f.eks. 5,5-dimetylhydantoin. Poly(N-glycidyl) compounds include, for example, those formed by hydrochlorination of the reaction products between epichlorohydrin and amines containing two amino hydrogen atoms such as aniline, n-butylamine, and bis(4-methylaminophenyl)methane; and N,N'-diglysidyl derivatives of cyclic alkylene urea compounds, such as e.g. ethylene urea and 1,3-propylene urea, and of hydantoins such as e.g. 5,5-dimethylhydantoin.
Eksempler på poly(S-glycidyl) forbindelser er di-S-glycidyl derivater av ditioler som f.eks. etan-1,2-ditiol og bis(4-merkaptometylfenyl) eter. Examples of poly(S-glycidyl) compounds are di-S-glycidyl derivatives of dithiols such as e.g. ethane-1,2-dithiol and bis(4-mercaptomethylphenyl) ether.
Polyepoksyder som har 1,2-epoksygruppene forbundet til forskjellige typer heteroatomer kan anvendes, f.eks. glycidyl eter-glycidylesteren av salisylsyre, N-glycidyl-N'-(2-glycidyloksypropyl)-5,5-dimetylhydantoin, og 2-glycidyloksy-1,3-bis(5,5-dimetyl-l-glyc idylhydantoin-3-yl) propan. Polyepoxides having the 1,2-epoxy groups connected to different types of heteroatoms can be used, e.g. the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3- yl) propane.
Polyepoksyder som inneholder ikke-terminale epoksygrupper kan også anvendes, som f.eks. vinylcykloheksendioksyd, limonendioksyd, dicyklopentadienoksyd, 4-oksatetracyklo [6, 2,1, 02' 7 ,03, 5] -undec-9-yl glycidyleter, bis (4-oksatetracyklo [6, 2,1,02'7,03'5 ] -undec-9-yl) eteren av etylenglykol, 3, 4-epoksycykloheksylmetyl 3',4'-epoksycyklo-heksankarboksylat og dets 6,6'-dimetyl derivat, bis(3,4-epoksycykloheksankarboksylat) av etylenglykol, og 3-(3,4-epoksycykloheksyl)-8,9-epoksy-2,4-dioksaspiro [5,5]undekan. Om ønsket kan også en blanding av diepoksyder benyttes. Polyepoksyder som inneholder mer enn to epoksygrupper kan benyttes, men reaksjonen mellom slike polyepoksyder og polyfunksjonelle reaktanter er vanskeligere, idet det foreligger en fare for gelering. Polyepoxides containing non-terminal epoxy groups can also be used, such as e.g. vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene oxide, 4-oxatetracyclo [6, 2,1, 02' 7 ,03, 5] -undec-9-yl glycidyl ether, bis (4-oxatetracyclo [6, 2,1,02'7,03' 5 ] -undec-9-yl) ether of ethylene glycol, 3, 4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative, bis(3,4-epoxycyclohexanecarboxylate) of ethylene glycol, and 3 -(3,4-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro [5,5]undecane. If desired, a mixture of diepoxides can also be used. Polyepoxides containing more than two epoxy groups can be used, but the reaction between such polyepoxides and polyfunctional reactants is more difficult, as there is a risk of gelation.
Foretrukne diepoksyder er diglycidyletere og diglycidyl-estere. Spesifikke foretrukne diepoksyder er diglycidyletere av 2,2-bis(4-hydroksyfenyl)propan eller bis(4-hydroksyfenyl)metan, som har et 1,2-epoksyinnhold på mer enn 1,0 ekvivalent pr. kilo. Preferred diepoxides are diglycidyl ethers and diglycidyl esters. Specific preferred diepoxides are diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane or bis(4-hydroxyphenyl)methane, which have a 1,2-epoxy content of more than 1.0 equivalent per kilo.
Den toverdige fenolen kan benyttes alene eller, om det ønskes, i nærvær av en forbindelse som reagerer med en epoksygruppe i polyepoksydet, men som ikke ville reagere videre slik at ytterligere kjede-forlengende reaksjoner unngås. Egnede slike "kjede-terminatorer" er sekundære monoaminer, monokarboksylsyrer og, mer spesielt, enverdige fenoler, p-tert.butylfenol er spesielt foretrukket. Dersom en kjede-terminator tilsettes må det være i en slik mengde at minst en epoksygruppe pr. gjennomsnittlig molekyl av polyepoksydet forblir fri , slik at den kan reagere med den toverdige fenolen. The dihydric phenol can be used alone or, if desired, in the presence of a compound which reacts with an epoxy group in the polyepoxide, but which would not react further so that further chain-extending reactions are avoided. Suitable such "chain terminators" are secondary monoamines, monocarboxylic acids and, more particularly, monohydric phenols, p-tert-butylphenol being particularly preferred. If a chain terminator is added, it must be in such a quantity that at least one epoxy group per average molecule of the polyepoxide remains free, allowing it to react with the divalent phenol.
Andre egnede harpikser (A) er de som oppnås ved polymerisering av en vinylmonomer i en epoksyharpiks som har en sekundær alkoholisk hydroksylgruppe, og deretter omsetning av det resulterende produktet med en flerverdig fenol som har en fri posisjon orto og/eller para ti], en fenolisk hydroksylgruppe slik at det dannes en fenol-terminert harpiks. Reaksjonen mellom epoksyharpiksen (som inneholder in situ polymerisert vinylmonomer) med den flerverdige fenolen, som fortrinnsvis er en toverdig fenol, kan utføres under tilsvarende betingelser som epoksyharpiks-flerverdig fenolreaksjonen beskrevet ovenfor, ved å benytte de samme toverdige fenoler og, om ønsket, kjede-terminatorer. Epoksyharpiksen som har en sekundær alkoholisk hydroksylgruppe kan være en polygly.cAdylester, polyglycidyleter, eller poly(N-glycidyl) forbindelse som beskrevet ovenfor avledet fra epiklorhydrin og et overskudd av henholdsvis polykarboksylsyren, den flerverdige alkoholen eller fenolen, eller nitrogenforbindelsen. Alternativt kan det være en harpiks oppnådd ved utvikling av en hvilken som helst av epoksyharpiksene beskrevet ovenfor, fortrinnsvis en harpiks som har to terminale glycidylgrupper, med en reaktant som har minst to grupper som er reaktive med epoksygruppene i relative mengder slik at det oppstår et epoksy-terminert produkt. Egnede slike fremmende reaktanter innbefatter polyfunksjonelle, fortrinnsvis di-funksjonelle, alkoholer, karboksylsyrer, aminer, merkap-taner og, spesielt, fenoler. Foretrukne toverdige fenoler er fenolene av formel I ovenfor. Betingelsene for fremmingsreaksjonen tilsvarer de som er beskrevet ovenfor for fremstillingen av et fenol-terminert reaksjonsprodukt av en epoksyharpiks og en toverdig fenol, med det unntak at forholdet mellom antall kjemiske ekvivalenter av fremmende reaktanter og epoksydharpiks vanligvis ligger innenfor området 1:1,02 til 1:1,6, spesielt 1:1,1 til 1:1,5. Other suitable resins (A) are those obtained by polymerizing a vinyl monomer in an epoxy resin having a secondary alcoholic hydroxyl group, and then reacting the resulting product with a polyhydric phenol having a free position ortho and/or para ti], a phenolic hydroxyl group to form a phenol-terminated resin. The reaction of the epoxy resin (containing in situ polymerized vinyl monomer) with the polyhydric phenol, which is preferably a dihydric phenol, can be carried out under similar conditions to the epoxy resin-polyhydric phenol reaction described above, using the same dihydric phenols and, if desired, chain terminators. The epoxy resin having a secondary alcoholic hydroxyl group may be a polygly.cAdyl ester, polyglycidyl ether, or poly(N-glycidyl) compound as described above derived from epichlorohydrin and an excess of the polycarboxylic acid, polyhydric alcohol or phenol, or nitrogen compound, respectively. Alternatively, it may be a resin obtained by developing any of the epoxy resins described above, preferably a resin having two terminal glycidyl groups, with a reactant having at least two groups which are reactive with the epoxy groups in relative amounts to produce an epoxy -terminated product. Suitable such promoting reactants include polyfunctional, preferably difunctional, alcohols, carboxylic acids, amines, mercaptans and, especially, phenols. Preferred divalent phenols are the phenols of formula I above. The conditions for the promotion reaction correspond to those described above for the preparation of a phenol-terminated reaction product of an epoxy resin and a dihydric phenol, except that the ratio of the number of chemical equivalents of promoting reactants to epoxy resin is usually in the range of 1:1.02 to 1 :1.6, especially 1:1.1 to 1:1.5.
Andre egnede harpikser (A) er de som oppnås ved polymerisering av en vinylmonomer i en fenoksyharpiks, dvs. en fenol-terminert harpiks analog med harpiksen fremstilt ved reaksjon mellom bisfenoldiglycidyleter og en bisfenol, men som oppnås direkte ved reaksjon mellom en bisfenol og epiklorhydrin. Den fenoksyharpiksdannende reaksjonen ut-føres vanligvis i et alkalisk medium ved å benytte til-nærmet ekvimolare mengder av bisfenol og epiklorhydrin, en kjedeterminator, som f.eks. enverdig fenol tilsettes når den ønskede molekylvekten er nådd. Other suitable resins (A) are those obtained by polymerization of a vinyl monomer in a phenoxy resin, i.e. a phenol-terminated resin analogous to the resin produced by reaction between bisphenol diglycidyl ether and a bisphenol, but obtained directly by reaction between a bisphenol and epichlorohydrin. The phenoxy resin-forming reaction is usually carried out in an alkaline medium by using approximately equimolar amounts of bisphenol and epichlorohydrin, a chain terminator, which e.g. monovalent phenol is added when the desired molecular weight is reached.
Som antydet ovenfor kan vinylmonomeren polymeriseres i den fenol-terminerte harpiksen eller i e/t epoksyharpiks- forstadium av denne. Monomeren, sammen med en fri radikal polymeriseringsinitiator, kan blandes med harpiksen eller med en oppløsning av harpiksen i et organisk oppløsnings-middel, som f.eks. n-butanol, 2-etoksyetanol, 2-butoksyetanol, etylacetat, toluen, xylen eller tetrahydrofuran. In situ polymerisering kan bevirkes ved å varme blandingen til en temperatur på 60 til 200°C, fortrinnsvis 100 til 150°C, vanligvis i et tidsrom på fra 1 til 10 timer. Monomeren kan benyttes i en slik mengde at det tilveiebringes opptil 50 vekt-% av harpiksen (A), dvs. den samlede vekten av den fenol-terminerte harpiksen og den polymeriserte vinylmonomeren. Det foretrekkes å benytte mengder slik at det tilveiebringes opptil 40 vekt-%, spesielt 10 til 30 vekt-% av harpiks (A) . Det vil si at der hvor monomeren polymeriseres i den fenol-terminerte harpiksen kan den benyttes i mengder på opptil 100 vekt-% av harpiksen, mengder opptil 67 vekt-%, spesielt 11 til 43 vekt-%, foretrekkes. Fri radikalinitiatoren er vanligvis tilstede i en mengde på fra 1 til 20 vekt-%, typisk 2 til 10 vekt-%, av monomeren. Monomeren og/eller initiatoren kan med fordel tilsettes til harpiksen i to eller flere trinn, hvor blandingen oppvarmes i 1 til 3 timer etter hver tilsats. As indicated above, the vinyl monomer can be polymerized in the phenol-terminated resin or in its e/t epoxy resin precursor. The monomer, together with a free radical polymerization initiator, can be mixed with the resin or with a solution of the resin in an organic solvent, such as e.g. n-butanol, 2-ethoxyethanol, 2-butoxyethanol, ethyl acetate, toluene, xylene or tetrahydrofuran. In situ polymerization can be effected by heating the mixture to a temperature of 60 to 200°C, preferably 100 to 150°C, usually for a period of from 1 to 10 hours. The monomer can be used in such an amount that it provides up to 50% by weight of the resin (A), i.e. the total weight of the phenol-terminated resin and the polymerized vinyl monomer. It is preferred to use quantities so that up to 40% by weight, in particular 10 to 30% by weight, of resin (A) is provided. That is, where the monomer is polymerized in the phenol-terminated resin it can be used in amounts up to 100% by weight of the resin, amounts up to 67% by weight, especially 11 to 43% by weight, are preferred. The free radical initiator is usually present in an amount of from 1 to 20% by weight, typically 2 to 10% by weight, of the monomer. The monomer and/or initiator can advantageously be added to the resin in two or more stages, where the mixture is heated for 1 to 3 hours after each addition.
Egnede vinylmonomerer innbefatter styrener, f.eks. styren selv, ring-substituerte styrener som f.eks. 4-metylstyren og 4-brom styren, og a - og 3-substituerte styrener som f.eks. a-metylstyren og 3-metylstyren; akrylsyre, metakrylsyre og estere derav, f.eks. alkylestere, spesielt de hvor alkylgruppene har fra 1 til 6 karbonatomer som f.eks. etylakrylat og metylmetakrylat, og hydroksyalkyl-estere, spesielt hydroksyetyl og hydroksypropylestere; akrylamid, metakrylamid og hydroksyalkylderivater derav som f.eks. N-metylolakrylamid; og vinylestere av karboksylsyrer som f.eks. vinylacetat og vinylpropionat. Blandinger av to eller flere vinylmonomerer kan benyttes. Spesielt foretrukne monomerer er styren, raetylmetakrylat og blandinger av disse to forbindelsene. Suitable vinyl monomers include styrenes, e.g. styrene itself, ring-substituted styrenes such as 4-methylstyrene and 4-bromostyrene, and α - and 3-substituted styrenes such as e.g. α-methylstyrene and 3-methylstyrene; acrylic acid, methacrylic acid and esters thereof, e.g. alkyl esters, especially those where the alkyl groups have from 1 to 6 carbon atoms such as e.g. ethyl acrylate and methyl methacrylate, and hydroxyalkyl esters, especially hydroxyethyl and hydroxypropyl esters; acrylamide, methacrylamide and hydroxyalkyl derivatives thereof such as e.g. N-methylolacrylamide; and vinyl esters of carboxylic acids such as e.g. vinyl acetate and vinyl propionate. Mixtures of two or more vinyl monomers can be used. Particularly preferred monomers are styrene, ethyl methacrylate and mixtures of these two compounds.
Fri radikal polymerisasjonsinitiatoren kan med fordel være et peroksyd, som kan være uorganisk eller organisk. Eksempler på uorganiske peroksyder er hydrogenperoksyd og persulfater, som f.eks. kalium- og natriumpersulfater. Eksempler på organiske peroksyder er acylperoksyder som f. eks. benzoylperoksyd, p--klorbenzoylperoksyd og t-butyl-perbenzoat, ketonperoksyder som f.eks. metyletylketonper-oksyd og cykloheksanonperoksyd, og hydroperoksyder som f.eks. kumenhydroperoksyd og t-butylhydroperoksyd. Andre egnede initiatorer innbefatter azoforbindelser som f.eks. azobis(isobutyronitril) og azobis( a-metylbutyronitril). Foretrukne initiatorer er benzoylperoksyd, kumenhydroperoksyd og azobis(isobutyronitril) . The free radical polymerization initiator can advantageously be a peroxide, which can be inorganic or organic. Examples of inorganic peroxides are hydrogen peroxide and persulphates, which e.g. potassium and sodium persulfates. Examples of organic peroxides are acyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and t-butyl perbenzoate, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and hydroperoxides such as e.g. cumene hydroperoxide and t-butyl hydroperoxide. Other suitable initiators include azo compounds such as azobis(isobutyronitrile) and azobis(α-methylbutyronitrile). Preferred initiators are benzoyl peroxide, cumene hydroperoxide and azobis(isobutyronitrile).
Aldehydet (B) som omsettes med harpiksen (A) og syren (eller saltet) (C) slik at det dannes et produkt som kan fortynnes med vann er fortrinnsvis et alifatisk aldehyd, spesielt et aldehyd som har fra 1 til 6 karbonatomer, selv om aromatiske aldehyder også kan benyttes, spesielt de som har fra 7 til 12 karbonatomer. Formaldehyd, som med fordel kan dannes in situ fra paraf ormaldehyd, er et spesielt foretrukket aldehyd. The aldehyde (B) which reacts with the resin (A) and the acid (or salt) (C) to form a water-dilutable product is preferably an aliphatic aldehyde, especially an aldehyde having from 1 to 6 carbon atoms, although aromatic aldehydes can also be used, especially those having from 7 to 12 carbon atoms. Formaldehyde, which can advantageously be formed in situ from paraformaldehyde, is a particularly preferred aldehyde.
Blandt nyttige syrer (C) finnes aminosulfon- og aminofosfonsyrer. Aminogruppen og sulfon- eller fosfonsyregruppen kan være forbundet med alifatiske-, aromatiske-, eller aralifatiske residuer. Egnede slike syrer innbefatter forbindelser av formelen: Useful acids (C) include aminosulfonic and aminophosphonic acids. The amino group and the sulphonic or phosphonic acid group can be connected with aliphatic, aromatic or araliphatic residues. Suitable such acids include compounds of the formula:
hvor R står for et hydrogenatom eller en alkylgruppe med fra 1 til 6 karbonatomer, where R stands for a hydrogen atom or an alkyl group with from 1 to 6 carbon atoms,
R står for en alifatisk-, aromatisk- eller aralifatisk to- eller treverdig hydrokarbongruppe med fra 1 til 10 karbonatomer som kan inneholde en fri sulfon- eller fosfonsyregruppe, og R stands for an aliphatic, aromatic or araliphatic di- or trivalent hydrocarbon group with from 1 to 10 carbon atoms which may contain a free sulfonic or phosphonic acid group, and
Y står for residuet av en sulfon- eller fosfonsyregruppe etter fjernelse av et hydrogenatom (dvs. -SO3- eller Y stands for the residue of a sulfonic or phosphonic acid group after removal of a hydrogen atom (ie -SO3- or
-P02H-). -P02H-).
Aminosulfonsyrer av formel II innbefatter sulfanilsyre, taurin, ortoanilinsyre, og 2-aminobenzen-l,4-disulfonsyre. Aminosulfonic acids of formula II include sulfanilic acid, taurine, orthoanilic acid, and 2-aminobenzene-1,4-disulfonic acid.
Aminofosfonsyrer av formel II innbefatter videre forbindelser av formelen: Aminophosphonic acids of formula II further include compounds of the formula:
hvor enten R<4> står for en alkylgruppe med fra 1 til 4 karbonatomer, en arylgruppe med fra 6 til 10 karbonatomer eller en fri fosfonsyregruppe av formelen -P(:0)(OH)2»where either R<4> stands for an alkyl group with from 1 to 4 carbon atoms, an aryl group with from 6 to 10 carbon atoms or a free phosphonic acid group of the formula -P(:0)(OH)2"
R star for et hydrogenatom, en alkylgruppe med fra 1 til 4 karbonatomer, eller en arylgruppe med fra 6 til 10 karbonatomer, og R stands for a hydrogen atom, an alkyl group with from 1 to 4 carbon atoms, or an aryl group with from 6 to 10 carbon atoms, and
R^ står for en kovalent binding eller en alkylengruppe med fra 1 til 4 karbonatomer, eller R^ stands for a covalent bond or an alkylene group with from 1 to 4 carbon atoms, or
R 4. og R 6 danner sammen med det karbonatom de er forbundet til en aromatisk ring og R^ er fraværende. R 4. and R 6 together with the carbon atom to which they are connected form an aromatic ring and R^ is absent.
Spesifikke aminofosfonsyrer av formel III innbefatter 2-åmino-l-fenyletylfosfonsyre, 1-aminoetylidenbis-(fosfon-syre) og aminofenylmetylenbis(fosfonsyre). Specific aminophosphonic acids of formula III include 2-amino-1-phenylethylphosphonic acid, 1-aminoethylidenebis(phosphonic acid) and aminophenylmethylenebis(phosphonic acid).
Andre nyttige syrer (C) er merkaptokarboksylsyrer. I disse syrene kan merkaptan og karboksylsyregrupper være forbundet med alifatiske-, aromatiske- eller aralifatiske residuer. Egnede merkaptokarboksylsyrer innbefatter syrer av formelen: Other useful acids (C) are mercaptocarboxylic acids. In these acids, mercaptan and carboxylic acid groups can be connected with aliphatic, aromatic or araliphatic residues. Suitable mercaptocarboxylic acids include acids of the formula:
hvor R står for en alifatisk-, aromatisk- eller aralifatisk toverdig gruppe med 1 til 10 karbonatomer som kan inneholde en ytterligere karboksylsyregruppe. where R stands for an aliphatic, aromatic or araliphatic divalent group with 1 to 10 carbon atoms which may contain a further carboxylic acid group.
Spesifikke syrer av formel IV er tioglykolsyre, 2-merkaptopropionsyre, 3-merkaptopropionsyre og tiomalin-syre. Specific acids of formula IV are thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and thiomalic acid.
Andre nyttige syrer (C) er aminokarboksylsyrer. Amino— og karboksylsyregruppene kan være forbundet med alifatiske-, aromatiske- eller aralifatiske residuer. Egnede aminokarboksylsyrer innbefatter syrer av formelen: Other useful acids (C) are aminocarboxylic acids. The amino and carboxylic acid groups can be connected with aliphatic, aromatic or araliphatic residues. Suitable aminocarboxylic acids include acids of the formula:
hvor R^ står for en alifatisk-, aromatisk- eller aralifatisk toverdig gruppe med fra 1 til 10 karbonatomer som kan inneholde en ytterligere karboksylsyregruppe og som fortrinnsvis er en alkylengruppe med fra 1 til 4 karbonatomer eller en fenylengruppe, og where R^ stands for an aliphatic, aromatic or araliphatic divalent group with from 1 to 10 carbon atoms which may contain a further carboxylic acid group and which is preferably an alkylene group with from 1 to 4 carbon atoms or a phenylene group, and
R Q staOr for et hydrogenatom, en gruppe av formelen: R Q stands for a hydrogen atom, a group of the formula:
eller en alkylgruppe med fra 1 til 6 karbonatomer som kan være substituert ved en ytterligere karboksylgruppe eller ved en gruppe av formelen -CH(R10)OH eller -CH(R10)0R12, under den forutsetning at R og R tilsammen ikke inneholder mer en en karboksylsyregruppe, or an alkyl group with from 1 to 6 carbon atoms which may be substituted by a further carboxyl group or by a group of the formula -CH(R10)OH or -CH(R10)0R12, provided that R and R together do not contain more than one carboxylic acid group,
R'<1>"<0> står for et hydrogenatom, en alkylgruppe med fra 1 til 4 karbonatomer, eller en arylgruppe med fra 6 til 1C karbonatomer, R'<1>"<0> stands for a hydrogen atom, an alkyl group with from 1 to 4 carbon atoms, or an aryl group with from 6 to 1C carbon atoms,
R^ står for et hydrogenatom, en karboksylsyregruppe, eller en alkylgruppe med fra 1 til 6 karbonatomer som kan være substituert med en karboksylsyregruppe eller med en gruppe av formelen -CH(R<10>)OH eller CH(R10)OR12, og R står for en alkylgruppe med fra 1 til 6 karbonatomer eller en alkoksyalkylgruppe hvor alkoksygruppen og alkylgruppen hver har fra 1 til 6 karbonatomer. R^ stands for a hydrogen atom, a carboxylic acid group, or an alkyl group with from 1 to 6 carbon atoms which may be substituted with a carboxylic acid group or with a group of the formula -CH(R<10>)OH or CH(R10)OR12, and R stands for an alkyl group with from 1 to 6 carbon atoms or an alkoxyalkyl group where the alkoxy group and the alkyl group each have from 1 to 6 carbon atoms.
Spesifikke syrer av formel V som kan benyttes innbefatter sarkosin, iminodieddiksyre, antranilinsyre, glycin, glutaminsyre, asparaginsyre og p-aminobenzosyre. Specific acids of formula V which may be used include sarcosine, iminodiacetic acid, anthranilic acid, glycine, glutamic acid, aspartic acid and p-aminobenzoic acid.
Salt som kan benyttes som komponent (C) i fremgangsmåten ifølge oppfinnelsen innbefatter kalium- og natriumsaltene av styren beskrevet ovenfor og av svovelsyre. Salt that can be used as component (C) in the method according to the invention includes the potassium and sodium salts of styrene described above and of sulfuric acid.
Fortrinnsvis er komponent (C) en aminokarboksylsyre eller en merkaptokarboksylsyre, spesifikke spesielt foretrukne syrer er glycin, glutaminsyre, asparaginsyre, p-aminobenzosyre, sarkosin og tioglykolsyre. Preferably, component (C) is an aminocarboxylic acid or a mercaptocarboxylic acid, specific particularly preferred acids being glycine, glutamic acid, aspartic acid, p-aminobenzoic acid, sarcosine and thioglycolic acid.
Reaksjonen mellom harpiksen (A), aldehydet (B) og syren eller saltet (C) kan bevirkes ved å oppvarme reaktantene, vanligvis i et inert oppløsningsmiddel, fortrinnsvis i nærvær av tilstrekkelig base til i det minste delvis å nøytralisere eventuell fri syre. Reaksjonstemperaturen ligger vanligvis i området fra 60 til 180°C, spesielt 75 til 140°C, og reaksjonen avsluttes vanligvis i løpet av et tidsrom på fra 15 min. til 8 timer. The reaction between the resin (A), the aldehyde (B) and the acid or salt (C) can be effected by heating the reactants, usually in an inert solvent, preferably in the presence of sufficient base to at least partially neutralize any free acid. The reaction temperature is usually in the range from 60 to 180°C, especially 75 to 140°C, and the reaction is usually completed within a period of from 15 min. to 8 hours.
Om nødvendig kan en base, eller ytterligere base, tilsettes til reaksjonsproduktet for å forbedre dets evne til å la seg fortynne med vann. Generelt nøytraliseres minst 25% av syregruppene som er tilstede i reaksjonsproduktet for å oppnå et produkt som fullt ut lar seg fortynne med vann, selv om omfanget av nøytraliseringen kan variere med egenskapene for reaktanten (C). If necessary, a base, or additional base, may be added to the reaction product to improve its ability to be diluted with water. In general, at least 25% of the acid groups present in the reaction product are neutralized to obtain a product that can be fully diluted with water, although the extent of neutralization may vary with the properties of the reactant (C).
Egnede inerte oppløsningsmidler innbefatter hydrokarboner, etere, alkoholer, og estere; blant disse er toluen, xylen, tetrahydrofuran, etylacetat, og spesielt 2-butoksyetanol og n-butanol, foretrukket. Egnede baser for den delvise nøytraliseringen innbefatter natriumhydroksyd, natrium-karbonat, kaliumhydroksyd, kaliumkarbonat, ammoniakk, tri-etylamin, og trietanolamin; 2-(dimetylamino)-2-metylpro-pan-l-ol og 2-(dimetylamino)etanol er spesielt foretrukket. Suitable inert solvents include hydrocarbons, ethers, alcohols, and esters; among these, toluene, xylene, tetrahydrofuran, ethyl acetate, and especially 2-butoxyethanol and n-butanol, are preferred. Suitable bases for the partial neutralization include sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia, triethylamine, and triethanolamine; 2-(dimethylamino)-2-methylpropan-1-ol and 2-(dimethylamino)ethanol are particularly preferred.
Vanligvis benyttes 0,3 til 2,0 mol av syren eller saltet Usually 0.3 to 2.0 mol of the acid or salt is used
(C) pr. mol av fenoliske hydroksylgrupper i harpiksen (A). Et overskudd av aldehydet (B) anvendes vanligvis, spesielt (C) per moles of phenolic hydroxyl groups in the resin (A). An excess of the aldehyde (B) is usually used, in particular
1,1 til 4,0 mol aldehyd pr. mol (C), fordi produktene da viser forbedret stabilitet ved lagring ved romtemperatur. Dersom harpiksen (A) har mer enn en fri posisjon orto 1.1 to 4.0 mol aldehyde per mol (C), because the products then show improved stability when stored at room temperature. If the resin (A) has more than one free ortho position
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eller para til en fenolisk hydroksylgruppe fører anvendelsen av et overskudd av et alifatisk aldehyd vanligvis til et produkt som har en hydroksyalkylgruppe knyttet til f endringen, som en følge av en reaksjon mellom den f enol-terminerte harpiksen og overskuddet av aldehyd, slik som den finner sted ved dannelsen av fenol-aldehydresoler under basiske forhold; der hvor aldehydet er formaldehyd er hydroksyalkylgruppen naturligvis en metylolgruppe. or para to a phenolic hydroxyl group, the application of an excess of an aliphatic aldehyde usually leads to a product having a hydroxyalkyl group attached to the f change, as a result of a reaction between the phenol-terminated resin and the excess of aldehyde, as it finds place in the formation of phenol-aldehyde resols under basic conditions; where the aldehyde is formaldehyde, the hydroxyalkyl group is naturally a methylol group.
De harpiksholdige materialene som fremstilles ifølge oppfinnelsen , .dvs. reaksjonsproduktene fra (A), (B) og (C), kan i form av varme-herdbare sammensetninger benyttes til å danne overflatebelegg. The resinous materials produced according to the invention, i.e. the reaction products from (A), (B) and (C) can be used in the form of heat-curable compositions to form surface coatings.
Det kan med utgangspunkt i produktet av fremgangsmåten ifølge oppfinnelsen fremstilles varme-herdbare sammensetninger som innbefatter 100-vektdeler av et reaksjonsprodukt av (A) , (B) og (C) , beregnet på basis av faststoffinnholdet (definert nedenfor) og 2 til 200 vektdeler, fortrinnvis 25 til 150 vektdeler, beregnet på basis av faststoffinnholdet, av en aminoplast, enf enol-formaldehydharpiks, eller et blokk-polyisocyanat, hvor aminoplasten eller fenol-formaldehyd-harpiksen har minst to grupper av formelen: Based on the product of the method according to the invention, heat-curable compositions can be prepared which include 100 parts by weight of a reaction product of (A), (B) and (C), calculated on the basis of the solids content (defined below) and 2 to 200 parts by weight , preferably 25 to 150 parts by weight, calculated on the basis of the solids content, of an aminoplast, phenol-formaldehyde resin, or a block polyisocyanate, wherein the aminoplast or phenol-formaldehyde resin has at least two groups of the formula:
forbundet direkte med et amidnitrogenatom eller atomer eller forbundet direkte til karbonatomer i en fenolring, hvor R står for et hydrogenatom eller en alkylgruppe med fra 1 til 6 karbonatomer. For anvendelse i slike varme-herdbare sammensetninger foretrekkes at reaks jonsproduktet av (A), (B) og (C) har alkoholiske hydroksylgrupper, som f.eks. sekundære alkoholiske hydroksylgrupper i residuet av formel -CH2-CH(OH)-CH2- i hovedkjeden av et produkt avledet fra en epoksyharpiks eller fenoksyharpiks, eller hydroksy-alkylgrupper festet til fenolringene som beskrevet ovenfor . connected directly to an amide nitrogen atom or atoms or connected directly to carbon atoms in a phenol ring, where R stands for a hydrogen atom or an alkyl group with from 1 to 6 carbon atoms. For use in such heat-curable compositions, it is preferred that the reaction product of (A), (B) and (C) has alcoholic hydroxyl groups, which e.g. secondary alcoholic hydroxyl groups in the residue of formula -CH2-CH(OH)-CH2- in the main chain of a product derived from an epoxy resin or phenoxy resin, or hydroxy-alkyl groups attached to the phenolic rings as described above.
Slike_sammensetninger i en form egnet for anvendesle som overflatebelegg vil vanligvis også inneholde vann og en mindre andel, sammen-' lignet med volumet av vannet, av et organisk oppløsnings-middel, som f.eks. en eter, alkohol, keton, eller ester, spesielt 2-butoksyetanol eller n-butanol. Metylolerte forbindelser som kan benyttes til å fremstille sammensetningene innbefatter urea-formaldehydkondensater, amino-triazin-formaldehydkondensater, spesielt melamin-formaldehyd og benzoguanamin-formaldehydkondensater, og fenol-formaldehydkondensater. Disse kan om ønsket foretres, dvs. n-butyletere kan benyttes. I mange tilfeller er de metylolerte forbindelsene og eterene derav ikke selv vann-oppløselige eller dispergerbare i vann. Inkorporering av et produkt fremstilt ifølge oppfinnelsen letter dispergeringen eller oppløsningen av slike materialer i vann, og gir stabile oppløsninger eller dispersjoner av blandingene. Such compositions in a form suitable for use as a surface coating will usually also contain water and a smaller proportion, compared to the volume of the water, of an organic solvent, such as e.g. an ether, alcohol, ketone, or ester, especially 2-butoxyethanol or n-butanol. Methylolated compounds which can be used to prepare the compositions include urea-formaldehyde condensates, amino-triazine-formaldehyde condensates, especially melamine-formaldehyde and benzoguanamine-formaldehyde condensates, and phenol-formaldehyde condensates. If desired, these can be preferred, i.e. n-butyl ethers can be used. In many cases, the methylolated compounds and ethers thereof are not themselves water-soluble or dispersible in water. Incorporation of a product made according to the invention facilitates the dispersion or dissolution of such materials in water, and provides stable solutions or dispersions of the mixtures.
Eksempler på egnede blokkpolyisocyanater (dvs. de som er stabile i den vandige dispersjonen ved romtemperatur,men som blir reaktive ved oppvarming) innbefatter di- og poly-isocyanater blokkdannet med kaprolaktam, et oksim (f.eks. cykloheksanonoksim), en enverdig fenol (f.eks. fenol selv, p-kresol, og p-tert.butylfenol), eller en enverdig alifatisk-, cykloalifatisk-, eller aralifatisk alkohol (f.eks. metanol, n-butanol, dekanol, 1-fenyletanol, 2-etoksyetanol, og 2-n-butoksyetanol). Egnede isocyanater innbefatter aromatiske di-isocyanater som f.eks. m-fenylen, 1,4-naftylen, 2,4- og 2,6-tolylen, og 4,4'-metylenbis-(fenylen) di-isocyanater, og også deres prepolymerer med glykoler (f.eks. etylen og propylenglykol), glyserol, tri-metylolpropan, pentaerytritol, dietylenglykol, og addi-sjonsprodukter av alkylenoksyder med disse alifatiske to-og flerverige alkoholene. Examples of suitable block polyisocyanates (i.e. those which are stable in the aqueous dispersion at room temperature, but which become reactive on heating) include di- and poly-isocyanates blocked with caprolactam, an oxime (e.g. cyclohexanone oxime), a monovalent phenol ( e.g. phenol itself, p-cresol, and p-tert.butylphenol), or a monohydric aliphatic, cycloaliphatic, or araliphatic alcohol (e.g. methanol, n-butanol, decanol, 1-phenylethanol, 2- ethoxyethanol, and 2-n-butoxyethanol). Suitable isocyanates include aromatic diisocyanates such as e.g. m-phenylene, 1,4-naphthylene, 2,4- and 2,6-tolylene, and 4,4'-methylenebis-(phenylene) diisocyanates, and also their prepolymers with glycols (e.g. ethylene and propylene glycol ), glycerol, trimethylolpropane, pentaerythritol, diethylene glycol, and addition products of alkylene oxides with these aliphatic two- and multi-chain alcohols.
Sammensetningene kan herdes ved oppvarming til 100°C til 275°C, fortrinnsvis 150°C til 225°C, i fra 30 sekunder til 1 time, fortrinnsvis fra 2 til 30 min. The compositions can be cured by heating to 100°C to 275°C, preferably 150°C to 225°C, for from 30 seconds to 1 hour, preferably from 2 to 30 minutes.
i in
Andre vann-oppløselige eller vann-dispergerbare filmdann-ende stoff kan også innbefattes, som f.eks. alkydharpikser og akrylharpikser. Mengden av slike materialer kan variere innen vide grenser, men bør ikke være så stor at de fordelaktige egenskapene for sammensetningene maskeres. Typisk anvendes tilstaser på opptil 50%, og fortrinnsvis opptil 30%, disse prosentandelene er basert på faststoffinnholdet i materialene. Other water-soluble or water-dispersible film-forming substances can also be included, such as e.g. alkyd resins and acrylic resins. The amount of such materials may vary within wide limits, but should not be so great as to mask the beneficial properties of the compositions. Typically, concentrations of up to 50%, and preferably up to 30%, are used, these percentages are based on the solids content of the materials.
Med betegnelsen "faststoffinnhold" som benyttes i foreliggende beskrivelse og krav, forstås det prosentvise residu som etterlates etter at en prøve på 1 g av materi-alet har vært oppvarmet på en åpen skål med diameter 5 cm i en ovn ved 120°C i 3 timer ved atmosfæretrykk. The term "solids content" used in the present description and claims is understood to mean the percentage residue left after a sample of 1 g of the material has been heated in an open dish with a diameter of 5 cm in an oven at 120°C for 3 hours at atmospheric pressure.
Når reaks jonsproduktet fra (A), (B) og (C) inneholder en hydroksyalkylgruppe som har fra 1 til 4 karbonatomer, som f. eks. en metylolgruppe, kan det varme-herdes uten til-setning av en aminoplast, en fenol-formaldehydharpiks, eller et blokkdannet polyisocyanat. When the reaction product from (A), (B) and (C) contains a hydroxyalkyl group having from 1 to 4 carbon atoms, such as e.g. a methylol group, it can be heat-cured without the addition of an aminoplast, a phenol-formaldehyde resin, or a block-formed polyisocyanate.
Belegning av en overflate kan utføres ved at Coating of a surface can be carried out by
flaten påføres reaksjonsproduktet fra (A), the surface is applied to the reaction product from (A),
(B) og (C) substituert med en hydroksyalkylgruppe -med fra 1 til 4 karbonatomer, og den belagte overflaten oppvarmes til en temperatur i området fra 100°C til 275°C, fortrinnsvis fra 150°C til 225°C, i fra 30 sekunder til 1 time, og fortrinnsvis fra 2 til 30 min. for å herde produktet. (B) and (C) substituted with a hydroxyalkyl group -having from 1 to 4 carbon atoms, and the coated surface is heated to a temperature in the range from 100°C to 275°C, preferably from 150°C to 225°C, for from 30 seconds to 1 hour, and preferably from 2 to 30 min. to harden the product.
Overflatene som skal belegges med sammensetningene om-talt ovenfor er fortrinnsvis av grunnbehandlet metall eller ubehandlet metall, spesielt et jernholdig metall, men kan også f. eks. være av tre eller av et varme-resistent syntetisk materiale. The surfaces to be coated with the compositions mentioned above are preferably of primed metal or untreated metal, especially a ferrous metal, but can also e.g. be made of wood or of a heat-resistant synthetic material.
Sammensetningene kan påføres ved neddykking, pensling, rulling, spraying (innbefattet elektrostatisk spraying), ved elektrolytisk avsetning, eller ved en hvilken som helst annen konvensjonell fremgangsmåte. Sammensetningene kan, om ønsket, innbefatte pigmenter og fargestoffer. Andre materialer som kan inkorporeres innbefatter drøye-midler som f.eks. kalsiumkarbonat, kalsiumsulfat, barium-sulfat, og magnesiumsilikat, overflateaktive midler, midler som forbedrer flyteevnen, og myknere. De kan også inneholde en sterk syre, f.eks. en aromatisk sulfonsyre eller dens salt med et amin eller ammoniakk, som katalys-ator. The compositions may be applied by dipping, brushing, rolling, spraying (including electrostatic spraying), by electrolytic deposition, or by any other conventional method. The compositions can, if desired, include pigments and dyes. Other materials that can be incorporated include retarding agents such as e.g. calcium carbonate, calcium sulfate, barium sulfate, and magnesium silicate, surfactants, flow improvers, and plasticizers. They can also contain a strong acid, e.g. an aromatic sulphonic acid or its salt with an amine or ammonia as catalyst.
Foreliggende oppfinnelse illusteres nærmere ved hjelp av følgende eksempler hvor alle prosentangivelser, angir vekt-%. The present invention is illustrated in more detail by means of the following examples where all percentages indicate weight-%.
Utgangsmaterialene som er benyttet i eksemplene ble fremstilt på følgende måte: The starting materials used in the examples were prepared in the following way:
Fenol I Phenol I
Epoksyharpiks I, en flytende diglycidylpolyeter av 2,2-bis(4-hydroksyfenyl)propan (359 g; epoksyinnhold 5,35 ekvivalenter/kg), 2,2-bis(4-hydroksyfenyl)propan (246 g), p-tert.butylfenol (20 g) og 10% vandig natriumhydroksyd-oppløsning (0,39 g) omrøres og oppvarmes under nitrogen til 180°C. Det molare forhold mellom epoksyharpiks og bisfenol og enverdig fenol er 1:1,14:0,14. En eksoterm reaksjon starter og temperaturen av blandingen øker spontant til 207°C. Blandingen avkjøles til 180°C og om-røres ved denne temperaturen i 3 1/2 time slik at man får fenol I, en fenolisk hydroksylgruppe-terminert harpiks som har et neglisjerbart innhold av epoksygrupper og en gjennomsnittlig molekylvekt på 1880. Epoxy resin I, a liquid diglycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane (359 g; epoxy content 5.35 equivalents/kg), 2,2-bis(4-hydroxyphenyl)propane (246 g), p-tert .butylphenol (20 g) and 10% aqueous sodium hydroxide solution (0.39 g) are stirred and heated under nitrogen to 180°C. The molar ratio between epoxy resin and bisphenol and monovalent phenol is 1:1.14:0.14. An exothermic reaction starts and the temperature of the mixture rises spontaneously to 207°C. The mixture is cooled to 180°C and stirred at this temperature for 3 1/2 hours to give phenol I, a phenolic hydroxyl group-terminated resin having a negligible content of epoxy groups and an average molecular weight of 1880.
Fenol II Phenol II
Epoksyharpiks I (2500 g) omrøres og varmes under nitrogen til 120°C. p-Tert.butylfenol (75 g) og 2,2-bis(4-hydroksy-fenyl)propan (897 g) tilsettes etterfulgt av en oppløsning som innbefatter natriumhydroksyd (0,25 g), vann (10,70 g) og metanol (3,50 g) og temperaturen økes til 160°C. Det molare forholdet mellom epoksyharpiks og bisfenol og enverdig fenol er 1:0,57:0,07. En eksoterm reaksjon starter og temperaturen av blandingen øker spontant til 210°C. Blandingen avkjøles til 190°C og omrøres ved denne temperaturen i ytterligere to timer, hvoretter den har et epoksyinnhold på 1,41 ekvivalenter/kg. 2,2-Bis(4-hyd-roksyfenyl)propan (865 g) tilsettes og blandingen omrøres i ytterligere 2 timer ved 190°C slik at man får fenol II, en fenolisk hydroksylgruppe-terminert harpiks som har et neglisjerbart innhold av epoksygrupper (ikke mer enn 0,045 ekvivalenter/kg) og en gjennomsnittlig molekylvekt på 1945. Epoxy resin I (2500 g) is stirred and heated under nitrogen to 120°C. p-Tert-butylphenol (75 g) and 2,2-bis(4-hydroxy-phenyl)propane (897 g) are added followed by a solution comprising sodium hydroxide (0.25 g), water (10.70 g) and methanol (3.50 g) and the temperature is increased to 160°C. The molar ratio of epoxy resin to bisphenol and monovalent phenol is 1:0.57:0.07. An exothermic reaction starts and the temperature of the mixture rises spontaneously to 210°C. The mixture is cooled to 190°C and stirred at this temperature for a further two hours, after which it has an epoxy content of 1.41 equivalents/kg. 2,2-Bis(4-hydroxyphenyl)propane (865 g) is added and the mixture is stirred for a further 2 hours at 190°C to give phenol II, a phenolic hydroxyl group-terminated resin having a negligible content of epoxy groups ( not more than 0.045 equivalents/kg) and an average molecular weight of 1945.
Fenol III Phenol III
Denne fremstilles på tilsvarende måte som fenol II, bort-sett fra at det molare forholdet mellom epoksyharpiks og den første bisfenoltilsatsen og enverdig fenol og den andre bisfenoltilsatsen er 1:0,58:0,04:0,55. Epoksyinnholdet etter den første bisfenoltilsatsen er 1,41 ekvivalenter/kg. Etter den andre bisfenoltilsatsen omrøres blandingen og oppvarmes til 195°C i 5 timer slik at man får fenol III, en fenolisk hydroksylgruppe-terminert harpiks som har et neglisjerbart innhold av epoksyd (ikke mer enn 0,05 ekvivalenter/kg) og en gjennomsnittlig molekylvekt på 2035. This is produced in a similar way to phenol II, except that the molar ratio between epoxy resin and the first bisphenol additive and monovalent phenol and the second bisphenol additive is 1:0.58:0.04:0.55. The epoxy content after the first bisphenol addition is 1.41 equivalents/kg. After the second bisphenol addition, the mixture is stirred and heated to 195°C for 5 hours to give phenol III, a phenolic hydroxyl group-terminated resin having a negligible epoxide content (not more than 0.05 equivalents/kg) and an average molecular weight in 2035.
Fenol IV Phenol IV
Epoksyharpiks I (338 g), 2,2-bis(4-hydroksyfenylJpropan (225 g) og 5% vandig natriumhydroksydoppløsning (0,5 g) omrøres og oppvarmes under nitrogen til 160°C. Det molare forhold mellom epoksyharpiks og bisfenol er 1:1,2. En eksoterm reaksjon starter og temperaturen stiger til 202°C. Blandingen avkjøles til 180°C og omrøres ved denne temperaturen i 2 timer. 2-Butoksyetanol tilsettes og reaksjonen fortsetter ved 180°C i ytterligere 3 timer slik at man får fenol IV, en fenolisk hydroksylgruppe-terminert harpiks som har en molekylvekt på 2900 og et neglisjerbart epoksyinnhold . Epoxy resin I (338 g), 2,2-bis(4-hydroxyphenyl)propane (225 g) and 5% aqueous sodium hydroxide solution (0.5 g) are stirred and heated under nitrogen to 160°C. The molar ratio between epoxy resin and bisphenol is 1 :1,2. An exothermic reaction starts and the temperature rises to 202°C. The mixture is cooled to 180°C and stirred at this temperature for 2 hours. 2-Butoxyethanol is added and the reaction continues at 180°C for a further 3 hours so that obtains phenol IV, a phenolic hydroxyl group-terminated resin having a molecular weight of 2900 and a negligible epoxy content.
Eksempel 1 Example 1
En oppløsning av fenol I (50 g; 0,027 mol) i 2-butoksyetanol (8,8 g) og n-butanol (10 g) oppvarmes til 120°C i en flensflaske utstyrt med en rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (8.8 g) and n-butanol (10 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of:
tilsettes i løpet av 2 timer via dryppetrakten til opp-løsningen av fenol I. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon benzoylperoksyd (0,2 g) tilsettes og reaksjonen fortsettes i enda en time. En andre monomer/initiatorblanding bestående av: tilsettes i løpet av 1 time. En ytterligere porsjon benzoylperoksyd (0,2 g) tilsettes og reaksjonen forsettes ved 120°C i to timer. Reaksjonsblandingen avkjøles til 100°C, deretter tilsettes: is added over the course of 2 hours via the dropping funnel to the solution of phenol I. The reaction is continued at 120°C for a further 2 hours before another portion of benzoyl peroxide (0.2 g) is added and the reaction is continued for another hour. A second monomer/initiator mixture consisting of: is added over the course of 1 hour. A further portion of benzoyl peroxide (0.2 g) is added and the reaction is continued at 120°C for two hours. The reaction mixture is cooled to 100°C, then added:
<*> 80% vandig oppløsning av 2-(dimetylamino)-2-metylpropan-l-ol. <*> 80% aqueous solution of 2-(dimethylamino)-2-methylpropan-1-ol.
Reaksjonsblandingen oppvarmes i en 1/2 time til 100°C, av-kjøles deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt innhold, 0,076 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer, ved dette tidspunktet ble innholdet av fritt formaldehyd bestemt til 0,7%. Det harpiksholdige produktet fortynnes med vann, slik at det oppstår en stabil emulsjon som har et faststoff innhold på 25% og som lar seg fortynne fullstendig med vann. The reaction mixture is heated for 1/2 hour to 100°C, then cooled to 90°C. Paraformaldehyde (2.5 g; 91% active content, 0.076 mol) is added and the temperature is maintained at 85°C for 6 hours, at which time the free formaldehyde content was determined to be 0.7%. The resinous product is diluted with water, so that a stable emulsion is formed which has a solids content of 25% and which can be diluted completely with water.
Eksempel 2 Example 2
En oppløsning av fenol IV (.50 g; 0,018 mol) i 2-butoksyetanol (10 g) og n-butanol (10 g) oppvarmes til 120°C i en flensflaske utstyrt med rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: A solution of phenol IV (.50 g; 0.018 mol) in 2-butoxyethanol (10 g) and n-butanol (10 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of:
tilsettes i løpet av 2 timer via dryppetrakten til opp-løsningen av fenol IV. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon benzoylperoksyd (0,2 g) tilsettes og reaksjonen fortsetter enda en time. En andre monomer/initiatorblanding bestående av: tilsettes i løpet av 1 time. En ytterligere porsjon benzoylperoksyd (0,2 g) tilsettes og reaksjonen forsettes ved 120°C |i 2 timetf. Reaksjonsblandingen avkjøles til 100°C og følgende blanding tilsettes: is added over the course of 2 hours via the dropping funnel to the solution of phenol IV. The reaction is continued at 120°C for a further 2 hours before another portion of benzoyl peroxide (0.2 g) is added and the reaction continues for another hour. A second monomer/initiator mixture consisting of: is added over the course of 1 hour. A further portion of benzoyl peroxide (0.2 g) is added and the reaction is continued at 120°C for 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Reaksjonsblandingen oppvarmes til 100°C i en halv time, og avkjøles deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt /innhold, ,0,076 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer, ved dette tidspunktet måles innholdet av fritt formaldehyd til 0,8%. Fritt styren kan ikke detekteres i produktet ved hjelp av gass-kromatografi. Etter tilsats av ytteligere DMAMP-80 (1,8 g) fortynnes reaksjonsproduktet med vann slik at det oppstår en stabil emulsjon som har et faststoffinnhold på ca. 25% og fullstendig lar seg fortynne med vann. The reaction mixture is heated to 100°C for half an hour, and then cooled to 90°C. Paraformaldehyde (2.5 g; 91% active/content, .0.076 mol) is added and the temperature is maintained at 85°C for 6 hours, at which time the content of free formaldehyde is measured to be 0.8%. Free styrene cannot be detected in the product using gas chromatography. After addition of further DMAMP-80 (1.8 g), the reaction product is diluted with water so that a stable emulsion is formed which has a solids content of approx. 25% and completely can be diluted with water.
Eksempel 3 Example 3
En oppløsning av fenol I (50 g; 0,027 mol) i 2-butoksyetanol (10 g) og n-butanol (10 g) oppvarmes til 120°C i en flensflaske utstyrt med rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (10 g) and n-butanol (10 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of:
tilsettes i løpet av 2 timer via dryppetrakten til opp-løsningen av fenol I. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon azobis(isobutyroni-tril) (0,2 g) tilsettes og reaksjonen fortsetter i enda 1 time. En andre monomer/initiatorblanding bestående av: tilsettes i løpet av 1 time. Nok en porsjon azobis(iso-butyronitril ) (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i ytterligere 2 timer. Reaksjonsblandingen av-kjøles til 100°C og følgende blanding tilsettes: is added over the course of 2 hours via the dropping funnel to the solution of phenol I. The reaction is continued at 120°C for a further 2 hours before another portion of azobis(isobutyronitrile) (0.2 g) is added and the reaction continues for another 1 hour . A second monomer/initiator mixture consisting of: is added over the course of 1 hour. Another portion of azobis(iso-butyronitrile) (0.2 g) is added and the reaction is continued at 120°C for a further 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Blandingen oppvarmes til 100°C i 1/2 time, og avkjøles The mixture is heated to 100°C for 1/2 hour, and cooled
deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt innhold, 0,076 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer, ved dette tidspunkt ble innholdet av fritt formaldehyd målt til 0,3%. Det harpiksholdige produktet fortynnes med vann slik at det oppstår en stabil emulsjon som har 25% faststoffinnhold og fullt ut lar seg fortynne med vann. then to 90°C. Paraformaldehyde (2.5 g; 91% active content, 0.076 mol) is added and the temperature is maintained at 85°C for 6 hours, at which time the free formaldehyde content was measured to be 0.3%. The resinous product is diluted with water so that a stable emulsion is formed which has a solids content of 25% and can be fully diluted with water.
Eksempel 4 Example 4
En oppløsning av fenol I (50 g; 0,027 mol) i 2-butoksyetanol (10 g) og n-butanol (10 g) oppvarmes til 120°C i en flensflaske utstyrt med rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: tilsettes i løpet av to timer via dryppetrakten til opp-løsningen av fenol I. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes i enda en time. En andre monomer/initiatorblanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (10 g) and n-butanol (10 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of: is added over the course of two hours via the dropping funnel to the solution of phenol I. The reaction is continued at 120°C for a further 2 hours before another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued for another one hour. A second monomer/initiator mixture consisting of:
tilsettes i løpet av 1 time. Nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i ytterligere 2 timer. Reaksjonsblandingen avkjøles is added within 1 hour. Another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued at 120°C for a further 2 hours. The reaction mixture is cooled
til 100°C og følgende blanding tilsettes: to 100°C and the following mixture is added:
Reaksjonsblandingen oppvarmes til 100°C i 1/2 time, oq avkjøles deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt innhold, 0,076 mol) tilsettes og temperaturen holdes ved 80°C i 6 timer, ved dette tidspunktet måles innholdet av fritt formaldehyd til 0,45%. Det harpiksholdige produktet fortynnes med vann slik at det oppstår en stabil emulsjon som har et faststoff innhold på 25% og fullt ut lar seg fortynne med vann. The reaction mixture is heated to 100°C for 1/2 hour, and then cooled to 90°C. Paraformaldehyde (2.5 g; 91% active content, 0.076 mol) is added and the temperature is maintained at 80°C for 6 hours, at which time the content of free formaldehyde is measured to be 0.45%. The resinous product is diluted with water so that a stable emulsion is formed which has a solids content of 25% and can be fully diluted with water.
Eksempel 5 Example 5
En oppløsning av fenol III (500 g; 0,25 mol) i 2-butoksyetanol (100 g) og n-butanol (100 g) oppvarmes til 120°C i en flensflaske utstyrt med rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: A solution of phenol III (500 g; 0.25 mol) in 2-butoxyethanol (100 g) and n-butanol (100 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of:
tilsettes i løpet av 2 timer via dryppetrakten til opp-løsningen av fenol III. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon kumenhydroperoksyd (2,0 g) tilsettes og reaksjonen fortsettes i enda en time. En andre monomer/initiatorblanding bestående av: tilsettes i løpet av 1 time. Nok en porsjon kumenhydroperoksyd (2,0 g) tilsettes og reaksjonen fortsettes ved 120°C i ytterligere 2 timer. Reaksjonsblandingen avkjøles til 100°C og følgende blanding tilsettes: is added over the course of 2 hours via the dropping funnel to the solution of phenol III. The reaction is continued at 120°C for a further 2 hours before another portion of cumene hydroperoxide (2.0 g) is added and the reaction is continued for another hour. A second monomer/initiator mixture consisting of: is added over the course of 1 hour. Another portion of cumene hydroperoxide (2.0 g) is added and the reaction is continued at 120°C for a further 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Reaksjonsblandingen oppvarmes til 100°C i 30 min., og avkjøles deretter til 90°C. Paraformaldehyd (25 g; 91% aktivt innhold, 0,76 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer, ved dette tidspunktet ble innholdet av fritt formaldehyd målt til 0,45%. Det harpiksholdige produktet fortynnes med vann slik at det dannes en stabil emulsjon som har et faststoff innhold på 25% og fullt ut lar seg fortynne med vann. The reaction mixture is heated to 100°C for 30 min., and then cooled to 90°C. Paraformaldehyde (25 g; 91% active content, 0.76 mol) is added and the temperature is maintained at 85°C for 6 hours, at which time the free formaldehyde content was measured to be 0.45%. The resinous product is diluted with water so that a stable emulsion is formed which has a solids content of 25% and can be fully diluted with water.
Eksempel 6 Example 6
En oppløsning av fenol I (50 g; 0,027 mol) i 2-butoksyetanol (10 g) og n-butanol (10 g) oppvarmes til 120°C i en flensflaske utstyrt med rører, kondensator, dryppetrakt og termometer. En monomer/initiatorblanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (10 g) and n-butanol (10 g) is heated to 120°C in a flask fitted with a stirrer, condenser, dropping funnel and thermometer. A monomer/initiator mixture consisting of:
tilsettes i løpet av 2 timer via dryppetrakten til opp-løsningen av fenol I. Reaksjonen fortsettes ved 120°C i ytterligere 2 timer før nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes i 2 timer. En andre monomer/initiatorblanding bestående av: tilsettes i løpet av 1 time. Nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsetter ved 120°C i ytterligere 2 timer. Reaksjonsblandingen avkjøles til 100°C og følgende blanding tilsettes: is added over the course of 2 hours via the dropping funnel to the solution of phenol I. The reaction is continued at 120°C for a further 2 hours before another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued for 2 hours. A second monomer/initiator mixture consisting of: is added over the course of 1 hour. Another portion of cumene hydroperoxide (0.2 g) is added and the reaction continues at 120°C for a further 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Reaksjonsblandingen oppvarmes til 100°C i 1/2 time, og avkjøles deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt innhold, 0,076 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer. Det harpiksholdige produktet fortynnes med vann slik at det dannes en stabil emulsjon som har et faststoff innhold på 25% og fullt ut lar seg fortynne med vann. The reaction mixture is heated to 100°C for 1/2 hour, and then cooled to 90°C. Paraformaldehyde (2.5 g; 91% active content, 0.076 mol) is added and the temperature is maintained at 85°C for 6 hours. The resinous product is diluted with water so that a stable emulsion is formed which has a solids content of 25% and can be fully diluted with water.
Eksempel 7 Example 7
En oppløsning av fenol III (320 g; 0,13 mol) i 2-butoksyetanol (155,4 g) og n-butanol (155,4 g) oppvarmes til 110°C i en flensflaske utstyrt med rører, kondensator, nitrogenspyler, temperaturregistering og innløp fra en peristaltisk tilførselspumpe. Benzoylperoksyd (70% i vann, 0,55 g) tilsettes og styrentilførselen startes ved 0,8 ml min.<->"'", 80 g styren tilsettes i løpet av 90 min. og ytterligere tilsatser av benzoylperoksyd gjøres etter 30 min. (1,55 g), 60 min. (1,55 g) og 90 min. (3,1 g). Blandingen oppvarmes til 110°C i ytterligere 2 timer. Asparaginsyre (21,2 g, 0,16 mol) og 2-(dimetylamino)-2-metylpropan-l-ol (80% vandig oppløsning, 23,6 g; 0,16 mol) tilsettes og blandingen omrøres i 15 min., og avkjøles deretter til 80°C. Paraformaldehyd (14,2 g; aktivt innhold 91%, 0,34 mol) tilsettes og temperaturen holdes ved 80°C i 3 timer. Den harpiksholdige produktoppløsningen som oppnås har et faststoffinnhold på 56% og lar seg fullt ut fortynne med vann. A solution of phenol III (320 g; 0.13 mol) in 2-butoxyethanol (155.4 g) and n-butanol (155.4 g) is heated to 110°C in a flanged flask equipped with a stirrer, condenser, nitrogen purge, temperature recording and inlet from a peristaltic feed pump. Benzoyl peroxide (70% in water, 0.55 g) is added and the styrene supply is started at 0.8 ml min.<->"'", 80 g of styrene is added during 90 min. and further additions of benzoyl peroxide are made after 30 min. (1.55 g), 60 min. (1.55 g) and 90 min. (3.1 g). The mixture is heated to 110°C for a further 2 hours. Aspartic acid (21.2 g, 0.16 mol) and 2-(dimethylamino)-2-methylpropan-1-ol (80% aqueous solution, 23.6 g; 0.16 mol) are added and the mixture is stirred for 15 min. , and then cooled to 80°C. Paraformaldehyde (14.2 g; active content 91%, 0.34 mol) is added and the temperature is maintained at 80°C for 3 hours. The resulting resinous product solution has a solids content of 56% and can be fully diluted with water.
Eksempel 8 Example 8
Eksempel 7 gjentas ved å benytte fenol I (320 g; 0,17 mol) i stedet for fenol III. Produktet har et faststoffinnhold på 56% og lar seg fullt ut fortynne med vann. Example 7 is repeated by using phenol I (320 g; 0.17 mol) instead of phenol III. The product has a solids content of 56% and can be fully diluted with water.
Eksempel 9 Example 9
En epoksyharpiks som har et epoksyinnhold på 1,52 ekvivalenter/kg (499,1 g), fremstilt ved å omsette epoksyharpiks I med 2,2-bis(4-hydroksyfenyl)propan, oppvarmes til 145°C og en blanding av styren (99,8 g) og kumenhydroperoksyd (80% oppløsning i kumen, 5,5 g) tilsettes via den peristaltiske pumpen i løpet av et tidsrom på 1 time. Reaksjonen fortsettes ved 145°C i ytterligere 2 timer. 2,2-Bis(4-hydroksyfenylJpropan (124,5 g, 0,55 mol) tilsettes og temperaturen av reaksjonsblandingen heves sakte til 190°C i løpet av et tidsrom på 5 timer, hvoretter epoksyinnholdet er neglisjerbart. 2-Butoksyetanol (285,2 g) og n-butanol (285,2 g) tilsettes og den resulterende oppløsningen avkjøles til 110°C. Asparaginsyre (36,4 g, An epoxy resin having an epoxy content of 1.52 equivalents/kg (499.1 g), prepared by reacting epoxy resin I with 2,2-bis(4-hydroxyphenyl)propane, is heated to 145°C and a mixture of styrene ( 99.8 g) and cumene hydroperoxide (80% solution in cumene, 5.5 g) are added via the peristaltic pump over a period of 1 hour. The reaction is continued at 145°C for a further 2 hours. 2,2-Bis(4-hydroxyphenyl)propane (124.5 g, 0.55 mol) is added and the temperature of the reaction mixture is slowly raised to 190°C over a period of 5 hours, after which the epoxy content is negligible. 2-Butoxyethanol (285 .2 g) and n-butanol (285.2 g) are added and the resulting solution is cooled to 110° C. Aspartic acid (36.4 g,
0,27 mol) og 2-(dimetylamino)-2-metylpropan-l-ol (80% vandig oppløsning, 40,6 g;0,28 mol) tilsettes og reaksjonsblandingen avkjøles til 80°C. Paraformaldehyd (24,3 g; 91% aktivt innhold, 0,74 mol) tilsettes og temperaturen av blandingen holdes ved 80°C i 3 timer. Den resulterende oppløsningen av harpiksholdig produkt har et faststoff innhold på 56% og lar seg fullt ut fortynne med vann. 0.27 mol) and 2-(dimethylamino)-2-methylpropan-1-ol (80% aqueous solution, 40.6 g; 0.28 mol) are added and the reaction mixture is cooled to 80°C. Paraformaldehyde (24.3 g; 91% active content, 0.74 mol) is added and the temperature of the mixture is maintained at 80°C for 3 hours. The resulting solution of resinous product has a solids content of 56% and can be fully diluted with water.
Eksempel 10 Example 10
Fenol II (722 g; 0,37 mol) oppløses i 2-butoksyetanol (3 50,6 g) og n-butanol (350,6 g) ved 120°C. En oppløsning som innbefatter kumenhydroperoksyd (80% oppløsning i kumen, 7,6 g) og styren (144,4 g) tilsettes via en peristaltisk pumpe i løpet av 150 min., og blandingen oppvarmes til 120°C i ytterligere 3 timer. Oppløsningen av-kjøles til 110°C og asparaginsyre (47,8 g; 0,36 mol) og 2-(dimetylamino)-2-metylpropan-l-ol (80% vandig oppløsning; 53,2 g; 0,36 mol) tilsettes. Etter avkjøling til 80°C tilsettes paraformaldehyd (32,0 g; 91% aktivt innhold, 0,97 mol) og blandingen omrøres ved 80°C i 3 timer. Den resulterende harpiksholdige produktoppløsningen har et faststoff innhold på 58% og lar seg fullt ut fortynne med vann. En blanding av produktet med en kommersielt tilgjengelig butylert urea-formaldehydharpiks med faststoffinnhold 53%, ved et faststofforhold på 90:10, ga ved for-tynning med vann en emulsjon som hadde et faststoffinnhold på 25% og var velegnet for bruk som en belegningssammen-setning, og hadde en viskositet (Ford B4 kopp) på 13 sekunder. Phenol II (722 g; 0.37 mol) is dissolved in 2-butoxyethanol (350.6 g) and n-butanol (350.6 g) at 120°C. A solution containing cumene hydroperoxide (80% solution in cumene, 7.6 g) and styrene (144.4 g) is added via a peristaltic pump over 150 min., and the mixture is heated to 120°C for a further 3 hours. The solution is cooled to 110°C and aspartic acid (47.8 g; 0.36 mol) and 2-(dimethylamino)-2-methylpropan-1-ol (80% aqueous solution; 53.2 g; 0.36 mol) ) is added. After cooling to 80°C, paraformaldehyde (32.0 g; 91% active content, 0.97 mol) is added and the mixture is stirred at 80°C for 3 hours. The resulting resinous product solution has a solids content of 58% and can be fully diluted with water. A mixture of the product with a commercially available butylated urea-formaldehyde resin having a solids content of 53%, at a solids ratio of 90:10, on dilution with water gave an emulsion which had a solids content of 25% and was suitable for use as a coating composition. sentence, and had a viscosity (Ford B4 cup) of 13 seconds.
Eksempel 11 Example 11
En oppløsning av fenol I (50 g; 0,02 7 mol) i 2-butoksyetanol (10 g) og n-butanol (10 g) oppvarmes til 120°C. En monomer/initiatorblanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (10 g) and n-butanol (10 g) is heated to 120°C. A monomer/initiator mixture consisting of:
tilsettes dråpevis til oppløsningen i løpet av 2 timer. Reaksjonen fortsettes ved 120°C i ytterligere en time før nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i 2 timer. En andre monomer/initiatorblanding bestående av: > tilsettes dråpevis i løpet av 1 time. Nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i ytterligere 2 timer. Reaksjonsblandingen avkjøles til 100°C og følgende blanding tilsettes: is added dropwise to the solution over 2 hours. The reaction is continued at 120°C for a further hour before another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued at 120°C for 2 hours. A second monomer/initiator mixture consisting of: > is added drop by drop over the course of 1 hour. Another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued at 120°C for a further 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Blandingen holdes ved 100°C i 30 min., og avkjøles deretter til 90°C. Paraformaldehyd (2,5 g; 91% aktivt innhold, 0,076 mol) tilsettes og temperaturen holdes ved 85°C i 6 timer, ved dette tidspunktet måles innholdet av fritt formaldehyd til 0,6%. Den resulterende oppløsningen av harpiksholdig produkt lar seg fullt ut fortynne med vann. En blanding av produktet med en kommersielt tilgjengelig butylert urea-formaldehydharpiks som har et faststoffinnhold på 53% i faststofforhold på 90:10, gir når den fortynnes med vann en emulsjon som har et faststoffinnhold på 25% og er velegnet for bruk som en belegningssammen-setning, emulsjonen har en viskositet (Ford B4 kopp) på 26 sekunder. The mixture is kept at 100°C for 30 min., and then cooled to 90°C. Paraformaldehyde (2.5 g; 91% active content, 0.076 mol) is added and the temperature is maintained at 85°C for 6 hours, at which time the content of free formaldehyde is measured to be 0.6%. The resulting solution of resinous product is fully dilutable with water. A mixture of the product with a commercially available butylated urea-formaldehyde resin having a solids content of 53% in a solids ratio of 90:10 gives, when diluted with water, an emulsion having a solids content of 25% and is suitable for use as a coating compound. sentence, the emulsion has a viscosity (Ford B4 cup) of 26 seconds.
Eksempel 12 Example 12
En oppløsning av fenol I (50 g; 0,027 mol) i 2-butoksyetanol (20 g) oppvarmes til 120°C. En monomer/initiator-blanding bestående av: A solution of phenol I (50 g; 0.027 mol) in 2-butoxyethanol (20 g) is heated to 120°C. A monomer/initiator mixture consisting of:
tilsettes dråpevis til oppløsningen i løpet av 2 timer. Reaksjonen fortsettes ved 120°C i ytterligere 1 time før nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i 2 timer. En andre monomer/initiatorblanding bestående av: tilsettes dråpevis i løpet av 1 time. Nok en porsjon kumenhydroperoksyd (0,2 g) tilsettes og reaksjonen fortsettes ved 120°C i ytterligere 2 timer. Reaksjonsblandingen avkjøles til 100°C og følgende blanding tilsettes: is added dropwise to the solution over 2 hours. The reaction is continued at 120°C for a further 1 hour before another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued at 120°C for 2 hours. A second monomer/initiator mixture consisting of: is added dropwise over the course of 1 hour. Another portion of cumene hydroperoxide (0.2 g) is added and the reaction is continued at 120°C for a further 2 hours. The reaction mixture is cooled to 100°C and the following mixture is added:
Blandingen holdes ved 100°C i 30 min., og avkjøles deretter til 90°C. Paraformaldehyd (5,5 g; 91% aktivt innhold, 0,168 mol) tilsettes og temperaturen heves til til-bakestrømningstemperaturen (137°C). Blandingen holdes ved tilbakestrøm.ningstemperaturen i 6 1/2 time, ved dette tidspunkt er innholdet av fritt formaldehyd 0,35%. Den resulterende oppløsning av harpiksholdig produkt lar seg fullt ut fortynne med vann. The mixture is kept at 100°C for 30 min., and then cooled to 90°C. Paraformaldehyde (5.5 g; 91% active content, 0.168 mol) is added and the temperature is raised to the reflux temperature (137°C). The mixture is held at the reflux temperature for 6 1/2 hours, at which time the free formaldehyde content is 0.35%. The resulting solution of resinous product can be fully diluted with water.
Eksempel 13 Example 13
En beleggsammensetning fremstilles ved å blande produktet fra eksempel 5 med en kommersielt tilgjengelig butylert fenolformaldehydharpiks, i form av en oppløsning (56% faststoffinnhold) i n-butanol som inneholder en mindre mengde toluen, ved et faststofforhold på 70:30. Sammen-setningen påføres en tinn-belagt stålplate ved virvel-belegning, dette gir et belegg som er 2 til 4 ym tykt. Platene oppvarmes til 200°C i 10 min. for å herde belegget. Det herdede belegget viser ingen defekter etter neddykking i kokende 2% eddiksyre i 6 timer. A coating composition is prepared by mixing the product of Example 5 with a commercially available butylated phenol formaldehyde resin, in the form of a solution (56% solids content) in n-butanol containing a small amount of toluene, at a solids ratio of 70:30. The composition is applied to a tin-coated steel plate by swirl coating, this gives a coating that is 2 to 4 um thick. The plates are heated to 200°C for 10 min. to harden the coating. The cured coating shows no defects after immersion in boiling 2% acetic acid for 6 hours.
Eksempel 14 Example 14
En beleggsammensetning fremstilles ved å blande produktet fra eksempel 7 med en kommersielt tilgjengelig butylert urea-formaldehydharpiks med et faststoffinnhold på 53%, i forhold 90:10 beregnet på basis av faststoffinnhold og fortynne blandingen med vann slik at det oppstår en emulsjon som har et faststoffinnhold på 25%. Viskositeten av emulsjonen måles. Emulsjonen påføres på en elektrolytisk tinnplate som en film mea*«tykkelse 2 til 4 y m og herdes ved oppvarming til 215°C i 3 min. Den resulterende belagte tinnplaten undersøkes. Resultatene fra viskositets-målingene og undersøkelsene av det herdede belegget er gjengitt nedenfor: A coating composition is prepared by mixing the product of Example 7 with a commercially available butylated urea-formaldehyde resin with a solids content of 53%, in a ratio of 90:10 calculated on the basis of solids content and diluting the mixture with water so that an emulsion is formed having a solids content of 25%. The viscosity of the emulsion is measured. The emulsion is applied to an electrolytic tin plate as a film mea*«thickness 2 to 4 µm and cured by heating to 215°C for 3 min. The resulting coated tin plate is examined. The results from the viscosity measurements and investigations of the cured coating are reproduced below:
Emulsjonsviskositet (Ford B4 kopp) Større enn 100 sek. Emulsion viscosity (Ford B4 cup) Greater than 100 sec.
<*> MEK gnidningsforsøket innbefatter at den belagte overflaten gis doble gnidninger med bomull gjennombløtt med metyletylketon. Resultatet angis som antall slike <*> The MEK rub test involves giving the coated surface double rubs with cotton soaked in methyl ethyl ketone. The result is stated as the number of such
gnidninger som kreves før belegget viser de første tegn på å være angrepet. rubbings required before the coating shows the first signs of being attacked.
kilebøyningstesten innbefatter støtbøying av prøven over en spindel som er 10 cm lang og har en ytre diameter på 6 mm ved den ene enden og smalner av mot et punkt på den the wedge bending test involves impact bending the specimen over a mandrel 10 cm long and having an outer diameter of 6 mm at one end and tapering to a point on the
andre enden. Prøven undersøkes så for å bestemme den prosentdel av lengden av prøven hvor belegget ikke skallet av. other end. The sample is then examined to determine the percentage of the length of the sample where the coating did not peel off.
Skravert kryss-adhes "jonstesten innbefatter at det med en kniv kuttes parallelle linjer 3 mm fra hverandre i det herdede belegget i en retning, og to andre parallelle linjer som skjærer disse ved en 90° vinkel. Et stykke klebende tape presses så over det snittede området. Tapen trekkes av med en rask og kontinuerlig bevegelse og området undersøkes med hensyn til fjernelse av belegg. Den prosentvise del av området hvorfra belegget ikke er fjernet angis. <4> pasteuriseringstestene innbefatter oppvarming av prøvene i vann, damp og de angitt syrene i de angitte tidsrom, den belagte overflaten undersøkes så med hensyn til hvitning og skravert-krysstesten gjentas. Adhesjonen og hvitningsegenskapene angis i henhold til en skala fra 0 til 5, hvor 0 angir utmerket adhesjon og ingen hvithet og 5 angir dårlige resultater for disse egenskapene. The hatched cross-adhesion test involves using a knife to cut parallel lines 3 mm apart in the hardened coating in one direction, and two other parallel lines cutting these at a 90° angle. A piece of adhesive tape is then pressed over the cut the area. The tape is pulled off with a rapid and continuous movement and the area is examined for the removal of coating. The percentage of the area from which the coating has not been removed is indicated. <4> the pasteurization tests include heating the samples in water, steam and the indicated acids in the indicated time periods, the coated surface is then examined for whitening and the hatched cross test is repeated.The adhesion and whitening properties are indicated according to a scale of 0 to 5, where 0 indicates excellent adhesion and no whitening and 5 indicates poor results for these properties.
Claims (13)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB848407283A GB8407283D0 (en) | 1984-03-21 | 1984-03-21 | Preparation of resinous products |
Publications (3)
Publication Number | Publication Date |
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NO851109L NO851109L (en) | 1985-09-23 |
NO162666B true NO162666B (en) | 1989-10-23 |
NO162666C NO162666C (en) | 1990-01-31 |
Family
ID=10558416
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO851109A NO162666C (en) | 1984-03-21 | 1985-03-20 | PROCEDURE FOR THE MANUFACTURING OF RESPECTABLE MATERIALS. |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0159288B1 (en) |
JP (1) | JPS60212405A (en) |
AU (1) | AU579616B2 (en) |
BR (1) | BR8501226A (en) |
CA (1) | CA1253991A (en) |
DE (1) | DE3562376D1 (en) |
GB (1) | GB8407283D0 (en) |
NO (1) | NO162666C (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS55116718A (en) * | 1979-03-02 | 1980-09-08 | Sumitomo Chem Co Ltd | Preparation of novel liquid polybutadiene-modified phenolic resin |
US4362853A (en) * | 1980-10-24 | 1982-12-07 | Ciba-Geigy Corporation | Resinous salts, their preparation, and their use in coatings |
DE3123536A1 (en) * | 1981-06-13 | 1982-12-30 | Basf Farben + Fasern Ag, 2000 Hamburg | BINDERS FOR CATHODICALLY DEPOSITABLE COATING MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
GB2127414B (en) * | 1981-12-24 | 1985-01-03 | Ciba Geigy Ag | Resinous salts their preparation and their use in coatings |
US4507446A (en) * | 1982-03-23 | 1985-03-26 | Ciba-Geigy Corporation | Water-soluble or water-dispersible resinous sulphur or phosphorus containing salts, their preparation, and their use in coatings |
-
1984
- 1984-03-21 GB GB848407283A patent/GB8407283D0/en active Pending
-
1985
- 1985-03-15 DE DE8585810113T patent/DE3562376D1/en not_active Expired
- 1985-03-15 EP EP19850810113 patent/EP0159288B1/en not_active Expired
- 1985-03-19 CA CA000476848A patent/CA1253991A/en not_active Expired
- 1985-03-20 NO NO851109A patent/NO162666C/en unknown
- 1985-03-20 AU AU40135/85A patent/AU579616B2/en not_active Ceased
- 1985-03-20 BR BR8501226A patent/BR8501226A/en unknown
- 1985-03-22 JP JP5767285A patent/JPS60212405A/en active Pending
Also Published As
Publication number | Publication date |
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AU579616B2 (en) | 1988-12-01 |
BR8501226A (en) | 1985-11-12 |
EP0159288B1 (en) | 1988-04-27 |
DE3562376D1 (en) | 1988-06-01 |
NO162666C (en) | 1990-01-31 |
NO851109L (en) | 1985-09-23 |
JPS60212405A (en) | 1985-10-24 |
EP0159288A3 (en) | 1986-11-05 |
CA1253991A (en) | 1989-05-09 |
EP0159288A2 (en) | 1985-10-23 |
GB8407283D0 (en) | 1984-04-26 |
AU4013585A (en) | 1985-09-26 |
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