NO147035B - MAGNESIUM OXIDE BASE GLASS SEPARATOR AND USE OF SAME - Google Patents
MAGNESIUM OXIDE BASE GLASS SEPARATOR AND USE OF SAME Download PDFInfo
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- NO147035B NO147035B NO771781A NO771781A NO147035B NO 147035 B NO147035 B NO 147035B NO 771781 A NO771781 A NO 771781A NO 771781 A NO771781 A NO 771781A NO 147035 B NO147035 B NO 147035B
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000395 magnesium oxide Substances 0.000 title abstract 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000000137 annealing Methods 0.000 abstract 1
- -1 acrylic compound Chemical class 0.000 description 79
- 239000000047 product Substances 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 66
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 51
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 39
- 239000011541 reaction mixture Substances 0.000 description 39
- 239000003549 soybean oil Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 37
- 235000012424 soybean oil Nutrition 0.000 description 36
- 239000002253 acid Substances 0.000 description 32
- 239000007795 chemical reaction product Substances 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 30
- GUGRBFQNXVKOGR-UHFFFAOYSA-N butyl hypochlorite Chemical group CCCCOCl GUGRBFQNXVKOGR-UHFFFAOYSA-N 0.000 description 29
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 26
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 25
- 239000000523 sample Substances 0.000 description 25
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 239000004342 Benzoyl peroxide Substances 0.000 description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 125000001309 chloro group Chemical group Cl* 0.000 description 13
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 238000005917 acylation reaction Methods 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 11
- 239000001530 fumaric acid Substances 0.000 description 11
- 235000011087 fumaric acid Nutrition 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000006317 isomerization reaction Methods 0.000 description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000032050 esterification Effects 0.000 description 9
- 239000011976 maleic acid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 7
- 230000010933 acylation Effects 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- SHDZTIZBSYDZSH-UHFFFAOYSA-N 2-methylprop-2-enoyl bromide Chemical compound CC(=C)C(Br)=O SHDZTIZBSYDZSH-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- WZHKDGJSXCTSCK-FNORWQNLSA-N (E)-Hept-3-ene Chemical compound CCC\C=C\CC WZHKDGJSXCTSCK-FNORWQNLSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000273930 Brevoortia tyrannus Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007824 aliphatic compounds Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- USHDBZLNUZHGOP-UHFFFAOYSA-N pentyl hypochlorite Chemical group CCCCCOCl USHDBZLNUZHGOP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229950011008 tetrachloroethylene Drugs 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 208000034874 Product colour issue Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- PZHNNJXWQYFUTD-UHFFFAOYSA-N phosphorus triiodide Chemical compound IP(I)I PZHNNJXWQYFUTD-UHFFFAOYSA-N 0.000 description 1
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- HSNQNPCNYIJJHT-ISLYRVAYSA-N trans-octadec-9-ene Chemical compound CCCCCCCC\C=C\CCCCCCCC HSNQNPCNYIJJHT-ISLYRVAYSA-N 0.000 description 1
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- PENRVBJTRIYHOA-UHFFFAOYSA-L zinc dithionite Chemical compound [Zn+2].[O-]S(=O)S([O-])=O PENRVBJTRIYHOA-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
- C23D5/10—Coating with enamels or vitreous layers with refractory materials
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Chemical Treatment Of Metals (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Glass Compositions (AREA)
Abstract
Glødningsseparator på magnesiumoksydbasis og anvendelse av samme.Magnesium oxide-based annealing separator and use of the same.
Description
Polymerisérbar nabo-akryloksyhalogenforbindelse. Polymerizable neighboring acryloxyhalogen compound.
Foreliggende oppfinnelse vedrører en polymerisérbar naboakryloksyhalogenforbindelse med strukturformelen: The present invention relates to a polymerizable neighboring acryloxyhalogen compound with the structural formula:
hvor R, er hydrogen, R2 er hydrogen eller where R 1 is hydrogen, R 2 is hydrogen or
O O
il ill
—COY, når Rg er hydrogen utvelges R3 fra hydrogen, alkyl med fra 1 til 4 karbonatomer, i alkoksy med fra 1 til 4 karbonatomer, halogen, fenyl, benzyl og når R» er —COY, when Rg is hydrogen, R3 is selected from hydrogen, alkyl with from 1 to 4 carbon atoms, in alkoxy with from 1 to 4 carbon atoms, halogen, phenyl, benzyl and when R» is
utvelges R„ fra hydrogen, halogen og R„ is selected from hydrogen, halogen and
alkyl med fra 1 til 4 karbonatomer, og Y utvelges fra en monovalent alifatisk gruppe med fra 1 til 18 karbonatomer og en monovalent aromatisk gruppe med fra 6 til 18 karbonatomer, R4 er hydrogen eller en monovalent alifatisk gruppe og fortrinnsvis er summen av karbonatomer i begge R4-grupper fra 8 til 22, og X er halogen. alkyl of from 1 to 4 carbon atoms, and Y is selected from a monovalent aliphatic group of from 1 to 18 carbon atoms and a monovalent aromatic group of from 6 to 18 carbon atoms, R 4 is hydrogen or a monovalent aliphatic group and preferably is the sum of carbon atoms in both R 4 groups from 8 to 22, and X is halogen.
Den foran angitte forbindelse fremstilles ved at en etylenisk umettet forbindelse med formelen omsettes med et alkylhypohalogenitt og en sur akrylforbindelse med strukturformelen: The above-mentioned compound is produced by reacting an ethylenically unsaturated compound with the formula with an alkyl hypohalogenite and an acidic acrylic compound with the structural formula:
hvor R,, R2, R,j og R4 har den ovenfor angitte betydning. where R1, R2, R1j and R4 have the above meaning.
Forskjellige litteratursteder, som f. eks. US-patent 2 054 814, US-patent 2 514 672, US-på-tent 2 511 870 og US-patent 2 947 766 beskriver halogenacylering av umettede forbindelser, som f. eks. isopren, akrylatestere og fettsyreestere med et alkylhalogenit og en mettet karboksylsyre. Ingen av disse patentskrifter åpenbarer imidlertid en slik reaksjon hvor det anvendes en etylenisk umettet karboksylsyre som acyleringsmiddel. Dette er ikke overraskende, da dobbeltbindingen i en umettet karboksylsyre er det logiske reaksjonssted for alkylhypohalogenit og et annet molekyl av umettet karboksyl-, syre. Hvis f. eks. oljesyre ble' erstattet med en mettet syre i fremgangsmåten som beskrevet i US-patent 2 514 672, så ville hovedparten av halogenaeyleringen finne sted ved dobbelbin-dingen i oljesyren (dvs. ett molekyl oljesyre og ett molekyl alkylhypohalogenit ville angripe en dobbeltbinding i et annet molekyl av oljesyre) og relativt lite av alkylakrylet ville delta i reaksjonen. Various literature sources, such as US Patent 2,054,814, US Patent 2,514,672, US Patent 2,511,870 and US Patent 2,947,766 describe halogen acylation of unsaturated compounds, such as isoprene, acrylate esters and fatty acid esters with an alkyl halide and a saturated carboxylic acid. However, none of these patents disclose such a reaction where an ethylenically unsaturated carboxylic acid is used as acylating agent. This is not surprising, as the double bond in an unsaturated carboxylic acid is the logical reaction site for alkyl hypohalide and another molecule of unsaturated carboxylic acid. If e.g. oleic acid was replaced by a saturated acid in the process as described in US patent 2,514,672, then most of the halogenation would take place at the double bond in the oleic acid (ie one molecule of oleic acid and one molecule of alkyl hypohalogenite would attack a double bond in another molecule of oleic acid) and relatively little of the alkyl acrylate would participate in the reaction.
Vi har nu funnet at den etyleniske dobbeltbinding i en sur akrylforbindelse (dvs. a, |3-etylenisk umettet monokarboksylsyre eller en halvester av en a, (3-etylenisk umettet dikar-boksylsyre) er overordentlig motstandsdyktig like overfor halogenacylering. I nærvær av langkjede te etylenisk umettede forbindelser ville den elektrofile natur av karboksygruppen i en a, |3-etylenisk umettet monokarboksylsyre og tilstedeværelsen av to slike elektrofile grupper i halvesteren av a, (3-etylenisk umettede di-karboksylsyrer, gjøre den etyleniske dobbeltbinding i disse sure akrylforbindelser overraskende motstandsdyktige like overfor angrep av alkylhypohalogeniter. Disse sure akrylforbm-delser har denne egenskap at de kan representeres av formelen:' We have now found that the ethylenic double bond in an acidic acrylic compound (ie a, |3-ethylenically unsaturated monocarboxylic acid or a half-ester of an a, (3-ethylenically unsaturated dicarboxylic acid) is remarkably resistant to halogen acylation. In the presence of long chain te ethylenically unsaturated compounds, the electrophilic nature of the carboxy group in an a, |3-ethylenically unsaturated monocarboxylic acid and the presence of two such electrophilic groups in the half-ester of a, (3-ethylenically unsaturated di-carboxylic acids, would make the ethylenic double bond in these acidic acrylic compounds surprising resistant to attack by alkyl hypohalogenites. These acidic acrylic compounds have the property that they can be represented by the formula:
hvor ' R. er ' hydrogen, R„ er hydrogen eller når R2* er-hydrogen' er R:) hydrogen el-leralkylmed fra' 1 til 4 karbonatomer, alkoksy med fra 1 til 4 karbonatomer, halogen,-' fenyl, benzyl eller '•' <;:> - - ; når R2OY, er R:! hydrogen, halogen eller alkyl- med fra 1 til 4 karbonatomer og Y er en énverdig alifatisk gruppe med fra 1 til 18 karbonatomer eller en aromatisk gruppe med fra 6 til 18 karbonatomer. De langkjedete etylenisk umettede forbindelser kan også representeres av formelen R CH2 —CH = CH — CH2 — R; hvor where R is hydrogen, R is hydrogen or when R 2 is hydrogen R is hydrogen or alkyl of from 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, phenyl, benzyl or '•' <;:> - - ; when R2OY, R:! hydrogen, halogen or alkyl with from 1 to 4 carbon atoms and Y is a monovalent aliphatic group with from 1 to 18 carbon atoms or an aromatic group with from 6 to 18 carbon atoms. The long-chain ethylenically unsaturated compounds can also be represented by the formula R CH2 —CH = CH — CH2 — R; where
er en alifatisk apen kjede .med ira iu tu ^4 karbonatomer, og R er hydrogen eller en énverdig alifatisk gruppe. is an aliphatic open chain .with ira iu tu ^4 carbon atoms, and R is hydrogen or a monovalent aliphatic group.
RE AKS JON SM EK AN ISME OG PRODUKTER RE AKS ION SM EK AN ISME AND PRODUCTS
Produktene i henhold til denne oppfinnelse fremstilles ved å bringe til reaksjon en sur akrylforbindelse (slik som definert ovenfor), en etylenisk umettet langkjedet alifatisk forbindelse (som definert ovenfor) og et alkylhypohalogenit. Den overveiende reaksjon er innfø-ringen av halogenatomet i hypohalogenit på et karbonatom i > C = C <-segmentet i den langkjedete forbindelse, idet det tydeligvis dannes et positivt karboniumion. Karboniumionet synes deretter å tiltrekke det negative anion i den sure akrylforbindelse, så at det dannes en nabo-akryloksyhalogenforbindelse. Alkoksyanionet fra alkylhypohalogenitet og hydrogenionet i den sure akrylforbindelse forenes så at det dannes en alkanol som et biprodukt, f. eks.: The products according to this invention are prepared by reacting an acidic acrylic compound (as defined above), an ethylenically unsaturated long-chain aliphatic compound (as defined above) and an alkyl hypohalogenite. The predominant reaction is the introduction of the halogen atom in hypohalogenite onto a carbon atom in the > C = C < segment of the long-chain compound, with a positive carbonium ion evidently being formed. The carbonium ion then appears to attract the negative anion in the acidic acrylic compound, so that a neighboring acryloxyhalogen compound is formed. The alkoxy anion from alkyl hypohalogenity and the hydrogen ion in the acidic acrylic compound combine to form an alkanol as a by-product, e.g.:
hvor R, R,, R2 og R3 er som definert ovenfor, R- er alkyl og X er halogen. where R, R1, R2 and R3 are as defined above, R- is alkyl and X is halogen.
Mens den ovenfor angitte ligning viser dannelsen av en enkelt forbindelse, så er forholdet det at det vanligvis fås en isomer blanding, da det positive halogenion kan forene seg med hvilket som helst av karbonatomene i den etyleniske gruppe. Reaksjonen gir også i mindre mengder biprodukter som kan representeres som følger, idet betydningen av R osv. er som tidligere anført: While the above equation shows the formation of a single compound, the ratio is that an isomeric mixture is usually obtained, as the positive halogen ion can combine with any of the carbon atoms in the ethylenic group. The reaction also gives in smaller quantities by-products which can be represented as follows, the meaning of R etc. being as previously stated:
En typisk fordeling (omtrent) av produktene i den ovenanførte reaksjonsblanding er som følger: 65 mol-pst. acryloxyhalogenderivat, 15 mol-pst. alkoxy-halogenderivat (B) og 20 mol-pst. allyllisk halogenderivat (C). Disse reaksjonsbiprodukter er forlikelige med halo-genacryloxyreaksjonsproduktet og plastiserer polymerene herav. A typical distribution (approximately) of the products in the above reaction mixture is as follows: 65 mole percent. acryloxyhalogen derivative, 15 mole percent. alkoxy-halogen derivative (B) and 20 mol wt. allylic halogen derivative (C). These reaction byproducts are compatible with the halogenacryloxy reaction product and plasticize the polymers thereof.
Komplekse blandinger av nabo-acryloxy-halogenforbindelser fåes særlig når poly-umettede forbindelser bringes til reaksjon med mindre enn en ekvivalentmengde av syreacrylforbindelsen. Forskjellige antall av acryloxygrupper ér knyttet til utgangsforbndelsene, og det fåes også stillingsisomerer. Følgelig fåes det ganske komplekse blandinger av reaksjonsprodukter, f. eks. fra sojabønneolje, som har i middel 4 ethylenisk umettede grupper pr. tri-glyceridmolekyl. Complex mixtures of neighboring acryloxy-halogen compounds are obtained in particular when polyunsaturated compounds are reacted with less than an equivalent amount of the acid acrylic compound. Different numbers of acryloxy groups are linked to the starting compounds, and positional isomers are also obtained. Consequently, rather complex mixtures of reaction products are obtained, e.g. from soybean oil, which has on average 4 ethylenically unsaturated groups per triglyceride molecule.
Som angitt ovenfor har de åcylerende sure acrylforbindelser i henhold til oppfinnelsen alle en ethylenisk umettet dobbéltbinding, som i seg selv er et teoretisk sted for halogenacylering. Jeg har imidlertid funnet at denne ethylenisk umettede dobbéltbinding er ganske stabil i nærvær av en langkjedet ethylenisk umettet forbindelse. I tilfelle av selve acrylsyren såvel som også methacrylsyren, synes denne motstand delvis å skyldes endestillingen av den ethyleniske dobbéltbinding, men mer viktig synes å være tilstedeværelsen av en elektrofil carboxylgruppe bundet til et carbonatom i ethylengruppen, hvilket gjør den ethyleniske dobbéltbinding en del av et konjugert dobbeltbindingssystem. a,p-kloracrylsyre og halv-esterne av maleinsyre og fumarsyre er ennå mindre tilbøyelige til å bli utsatt for halogenacylering som følge av tilstedeværelsen av en annen elektrofil gruppe på ett av carbonatomene i den ethyleniske gruppe. Hvilken som helst reaksjon mellom den sure acrylforbindelse og et annet molekyl av en sur acrylforbindelse gir produkter som er forlikelige med hovedreaksjonsproduktene og polyme-rer herav fjernes i de fleste tilfelle ved en alkalisk utvasking. As stated above, the acylating acid acrylic compounds according to the invention all have an ethylenically unsaturated double bond, which in itself is a theoretical site for halogen acylation. However, I have found that this ethylenically unsaturated double bond is quite stable in the presence of a long-chain ethylenically unsaturated compound. In the case of the acrylic acid itself as well as the methacrylic acid, this resistance seems to be partly due to the terminal position of the ethylenic double bond, but more important seems to be the presence of an electrophilic carboxyl group bound to a carbon atom in the ethylene group, which makes the ethylenic double bond part of a conjugate double bond system. a,p-chloroacrylic acid and the half-esters of maleic and fumaric acids are even less prone to undergo halogen acylation due to the presence of another electrophilic group on one of the carbon atoms of the ethylenic group. Any reaction between the acidic acrylic compound and another molecule of an acidic acrylic compound gives products which are compatible with the main reaction products and polymers thereof are removed in most cases by an alkaline leaching.
REAGENSENE THE REAGENTS
Hypohalogenitreagenset. The hypohalogen reagent.
Forskjellige alkylhypohalogeniter kan anvendes ved foreliggende oppfinnelse for halogenacyleringsreaksjonen, men det foretrekkes tertiære alkylhypohalogeniter, som tertiært butylhypoklorit og tertiært amylhypoklorit, da de er vesentlig mer stabile enn de, normale og sekundære alkylhypohalogeniter. F. eks. kan tertiært butylhypoklorit destilleres ved ca. 79°C eller høyere, og selv uten destillasjon kan det lagres (i mørket) ved romtemperatur i måneder uten' spaltning. Videre hindrer den store stør-relse av den tertiære alkylgruppe sterisk til-føyelsen av alkoxygruppene til det positive car-boniumion. Tertiært butylhypoklorit er særlig fordelaktig, fordi det kan fremstilles lett og billig. Various alkyl hypohalogenites can be used in the present invention for the halogen acylation reaction, but tertiary alkyl hypohalogenites, such as tertiary butyl hypochlorite and tertiary amyl hypochlorite, are preferred, as they are significantly more stable than the normal and secondary alkyl hypohalogenites. For example can tertiary butyl hypochlorite be distilled at approx. 79°C or higher, and even without distillation it can be stored (in the dark) at room temperature for months without' decomposition. Furthermore, the large size of the tertiary alkyl group sterically prevents the addition of the alkoxy groups to the positive carbonium ion. Tertiary butyl hypochlorite is particularly advantageous because it can be produced easily and cheaply.
Det langkjedete umettede reagens. The long-chain unsaturated reagent.
Noe mer detaljert kan den enverdige alifatiske gruppe R i den langkjedete ethylenisk umettede forbindelse inneholde andre grupper, som f. eks. hydroxylgrupper, carboxylgrupper, carboxylatgrupper, carbamylgrupper, aminogrupper, nitrilgrupper, carbamatgrupper, halo-gengrupper, acyloxygrupper, mercaptogrupper, alkoxygrupper, aryloxygrupper osv. De foretrakkede langkjedete ethylenisk umettede forbindelser i henhold til oppfinnelsen er de lett tilgjera gelige, naturlig forekommende glyceridoljer (som oppviser carboxylatgrupper), som f. eks. sojabønneolje, maisolje, bomullfrøolje, hampe-frøolje, tungolje, saflorolje, jordnøttolje, linfrø-olje, tobakkolje, torskeleverolje, sildeolje (eller menhadenolje), castorolje osv. Estere av andre umettede langkjedete syrer er også fordelaktige som utgangsmateriale, som f. eks. methylesteren av oljesyre, 2-ethylhexylesteren av linolinsyre, forskjellige estere av tallolje-fettsyrer osv. Gly-ceridene og andre estere er generelt stabile ved reaksjonen i henhold til oppfinnelsen, skjønt det kan fremstilles under rekasjonen små mengder av sekundære produkter (andre enn de foran nevnte). In more detail, the monovalent aliphatic group R in the long-chain ethylenically unsaturated compound may contain other groups, such as, for example hydroxyl groups, carboxyl groups, carboxylate groups, carbamyl groups, amino groups, nitrile groups, carbamate groups, halogen groups, acyloxy groups, mercapto groups, alkoxy groups, aryloxy groups, etc. The preferred long-chain ethylenically unsaturated compounds according to the invention are the easily obtainable, naturally occurring glyceride oils (which exhibit carboxylate groups ), like for example. soybean oil, corn oil, cotton seed oil, hemp seed oil, tung oil, safflower oil, peanut oil, linseed oil, tobacco oil, cod liver oil, herring oil (or menhaden oil), castor oil, etc. Esters of other unsaturated long-chain acids are also advantageous as starting materials, such as the methyl ester of oleic acid, the 2-ethylhexyl ester of linoleic acid, various esters of tall oil fatty acids, etc. The glycerides and other esters are generally stable in the reaction according to the invention, although small amounts of secondary products (other than those above) may be produced during the reaction mentioned).
På den annen side kan tilstedeværelsen av grupper i den langkjedete alifatiske forbindelse som er reaktive med alkylhypohalogenit, som f. eks. nitril- eller aminogrupper, eller som er reaktive med carboniumionet som dannes under halogenaeyleringen, som f. eks. hydroxyl- eller carboxylgrupper, føre til andre sidereaksjoner under halogenacyleringsreaksjonen. Ved de ut-førte forsøk er funnet at ethvert side-reaksjonsprodukt av denne art er forlikelig med hovedreaksjonsproduktene og polymerene herav. On the other hand, the presence of groups in the long-chain aliphatic compound which are reactive with alkyl hypohalide, such as e.g. nitrile or amino groups, or which are reactive with the carbonium ion formed during the halogenaylation, such as e.g. hydroxyl or carboxyl groups, lead to other side reactions during the halogen acylation reaction. In the tests carried out, it has been found that any side reaction product of this kind is compatible with the main reaction products and the polymers thereof.
De følgende er eksempler på andre av de ethylenisk umettede forbindelser som kan anvendes ved foreliggende oppfinnelse: 4-decen, 9-octadecen, 9-tetracosen, 10-hydroxydecen-2, 1-hydroxyoctadecen-9, 6-hydroxytetracosen-9, 1-klordecen-4, l-bromoctadecen-9, 1-klortetraco-sen-9, l-nitrildecen-4, l-nitriloctadecen-9, 1-ni-triltetracosen-9, l-aminodecen-4, 1-methylami-nooctadecen-9, l-dioctylaminotetracosen-9, 1-carbamyldecen-4, N-ethyl-l-carbamyloctadecen -9, N-dioctyl-l-carbamyltetracosen-9, 10-car-boxydecen-2, . oleinsyre, ricinolsyre, linolsyre, linolensyre, l-aceoxydecen-4, 1-fenoxyoctadecen -9, l-propoxyoctadecen-9 osv. The following are examples of other ethylenically unsaturated compounds that can be used in the present invention: 4-decene, 9-octadecene, 9-tetracocene, 10-hydroxydecene-2, 1-hydroxyoctadecene-9, 6-hydroxytetracocene-9, 1- chlorodecene-4, l-bromooctadecene-9, 1-chlorotetracocene-9, l-nitriledecene-4, l-nitrileoctadecene-9, 1-nitriletetracocene-9, l-aminodecene-4, 1-methylaminooctadecene- 9, l-dioctylaminotetracocene-9, 1-carbamyldecene-4, N-ethyl-l-carbamyloctadecene-9, N-dioctyl-l-carbamyltetracocene-9, 10-carboxydecene-2, . oleic acid, ricinoleic acid, linoleic acid, linolenic acid, l-aceoxydecene-4, 1-phenoxyoctadecene-9, l-propoxyoctadecene-9, etc.
Passende estere kan også fåes fra aromatiske hydroxy-forbindelser, som f. eks. fenol, cre-solene, resorcinol, hydrokinon, nafthol osv. Suitable esters can also be obtained from aromatic hydroxy compounds, such as e.g. phenol, cresolene, resorcinol, hydroquinone, naphthol, etc.
. Foreliggende oppfinnelse omfatter også. slike forbindelser, hvor esteren består av en flerverdig alkohol, som bare er delvis - forestret med . The present invention also includes such compounds, where the ester consists of a polyhydric alcohol, which is only partially - esterified with
en langkjedet carboxylsyre, f. eks. monoglyceri-der og diglycerider. Også innbefattet i oppfinnelsen er estere av en flerverdig alkohol, acy-lert delvis av mettede syrer. F. eks. kan glyce-rylhydroxygruppene i de foran nevnte monogly-cerider og diglycerider forestres med syrer som f. eks. eddiksyre, benzoesyre, stearinsyre osv. a long-chain carboxylic acid, e.g. monoglycerides and diglycerides. Also included in the invention are esters of a polyhydric alcohol, partially acylated by saturated acids. For example the glyceryl hydroxy groups in the above-mentioned monoglycerides and diglycerides can be esterified with acids such as e.g. acetic acid, benzoic acid, stearic acid, etc.
Syreacrylforbindelsen. The acid acrylic compound.
De følgende forbindelser er representative for de forskjellige sure acrylforbindelser, som kan anvendes som acyleringsmidler for foreliggende oppfinnelse: acrylsyre, methacrylsyre, ethacrylsyre, a-kloracrylsyre; a-bromacrylsyre, a-jodacrylsyre a-fenylacrylsyre; a-benzylacryl-syre; a-propoxyacrylsyre; methylhydrogenitaco-nat; methylhydrogenmaleat; methylhydrogenfumarat; methylhydrogenmesaconat; methylhyd-rogencitraconat; ethylhydrogenmaleat; ethyl-hydrogenf umarat; n-propylhydrogenmaleat; isopropylhydrcigenf umarat; n-butylhydrogen-maleat; tertiært butylhydrogenfumarat; iso-amylhydrogenfumarat; 4-methyl-2-pentylhydro-genfumarat; n-octylhydrogenmaleat; 2-ethyl-hexylhydrogenfumarat; decylhydrogenf umarat; laurylhydrogenmaleat; n-tridecylhydrogenma-leat; stearylhydrogenfumarat; octyldecylhydro-genmaleat; fenylhydrogenmaleat; p-cresylhyd-rogenfumarat; benzylhydrogenmaleat; nafthyl-hydrogenf umarat; éthylhydrogenklorf umarat; cyclohexylhydrogenmaleat; p-cresylhydrogen-maleat; p-klorfenylhydrogenmaleat; ethoxy-ethyl (Cellosolve) hydrogenfumarat; p-decyl-fenylhydrogenmaleat; allylhydrogenmaleat osv. The following compounds are representative of the various acidic acrylic compounds which can be used as acylating agents for the present invention: acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid; α-bromoacrylic acid, α-iodoacrylic acid α-phenylacrylic acid; α-benzylacrylic acid; α-propoxyacrylic acid; methylhydrogenitaconate; methyl hydrogen maleate; methyl hydrogen fumarate; methyl hydrogen mesaconate; methyl hydrogen citraconate; ethyl hydrogen maleate; ethyl hydrogen fumarate; n-propyl hydrogen maleate; isopropyl hydrogen fumarate; n-butyl hydrogen maleate; tertiary butyl hydrogen fumarate; iso-amyl hydrogen fumarate; 4-methyl-2-pentyl hydrogen fumarate; n-octyl hydrogen maleate; 2-ethyl-hexyl hydrogen fumarate; decylhydrogenfumarate; lauryl hydrogen maleate; n-tridecyl hydrogen maleate; stearyl hydrogen fumarate; octyldecyl hydrogen maleate; phenyl hydrogen maleate; p-cresyl hydrogen fumarate; benzyl hydrogen maleate; naphthyl hydrogen fumarate; ethyl hydrogen chlorofumarate; cyclohexyl hydrogen maleate; p-cresyl hydrogen maleate; p-chlorophenyl hydrogen maleate; ethoxy-ethyl (Cellosolve) hydrogen fumarate; p-decyl-phenyl hydrogen maleate; allyl hydrogen maleate etc.
Halv- estere av afi- ethylenisk umettede dicarboxylsyre. Half-esters of aphi-ethylenically unsaturated dicarboxylic acid.
Et viktig trekk ved halv-esterne av usubsti-tuerte a,|3-ethy.lenisk umettede a,§-dicarboxylsyrer (maleinsjfre og fumarsyre) er at egenskapene av acryloxyhalogen-polymeriserbare produkter basert på disse halv-estere, lett og på en billig måte kan variere ved å utvelge den ønskede alkohol, hvorav halv-esteren fremstilles. Når f. eks. halv-esteren er basert på en lavere alkohol, som f. eks. isopropanol, er sam-polymeriseringsproduktene av forbindelsen i henhold til oppfinnelsen med monomeret som f. eks. styren, mer faste enn når halv-esteren er basert på en høyere alkohol som f. eks. 2-ethylhexanol. Som en regel øker fleksibiliteten av sampolymerene etter som antallet av carbonatomer i alkoholen øker. Generelt danner aryl-halvestere hardere sampolymeriseringsprodukter enn. de tilsvarende alkylhalv-estere. Videre er halv-estere utledet fra halogen-acryloxyforbin-delser i henhold til oppfinnelsen, ofte likeså bil-lige eller billigere enn acrylsyre- og methacrylsyre-utledete forbindelser i henhold til oppfinnelsen. Produkter basert på isopropylhalv-esteren av fumarsyre eller maleinsyre har faktisk en avgjort økonomisk fordel like overfor mono-carboxylsyre-acrylforbindelser. Mens halv-esterne av substituerte a,|3-ethylenisk umettede a,(3-dicarboxylsyrer og halv-esteren av itaconsyre gir den samme produktfleksibilitet som maleat- og fumarat-halv-esterne, så er omkostningene ved deres anvendelse mindre tilfredsstillende. An important feature of the half-esters of unsubstituted α,|3-ethylenically unsaturated α,§-dicarboxylic acids (maleic acid and fumaric acid) is that the properties of acryloxyhalogen-polymerizable products based on these half-esters, easily and on a cheap way can vary by selecting the desired alcohol from which the half-ester is prepared. When e.g. The half-ester is based on a lower alcohol, such as isopropanol, are the co-polymerization products of the compound according to the invention with the monomer such as e.g. styrene, more solid than when the half-ester is based on a higher alcohol such as e.g. 2-ethylhexanol. As a rule, the flexibility of the copolymers increases as the number of carbon atoms in the alcohol increases. In general, aryl half-esters form harder copolymerization products than . the corresponding alkyl half-esters. Furthermore, half-esters derived from halogen-acryloxy compounds according to the invention are often just as cheap or cheaper than acrylic acid- and methacrylic acid-derived compounds according to the invention. Products based on the isopropyl half-ester of fumaric or maleic acid actually have a decided economic advantage over mono-carboxylic acid acrylic compounds. While the half-esters of substituted α,|3-ethylenically unsaturated α,(3-dicarboxylic acids and the half-ester of itaconic acid provide the same product flexibility as the maleate and fumarate half-esters, the costs of their use are less satisfactory.
Som påpekt tidligere, er halogen-acryloxy-forbindelsene basert på fumarsyre-halv-esterne en viktig klasse av polymeriserbare forbindelser 1 henhold til oppfinnelsen. Dette er særlig tilfelle med alkylhydrogenfumarater, som har fra As pointed out earlier, the halogen-acryloxy compounds based on the fumaric acid half-esters are an important class of polymerizable compounds 1 according to the invention. This is particularly the case with alkyl hydrogen fumarates, which have from
2 til 13 carbonatomer i alkylgruppen. Av en eller 2 to 13 carbon atoms in the alkyl group. Of one or
annen grunn som ikke kan forklares, er sampolymerene basert på fumarat-halv-esterne kla-rere, seigere og har en høyere strekkstyrke enn de tilsvarende produkter basert på maleat-halv-esterne. for another reason that cannot be explained, the copolymers based on the fumarate half-esters are clearer, tougher and have a higher tensile strength than the corresponding products based on the maleate half-esters.
Fremstilling av fumarat- halv- estere. Production of fumarate half-esters.
Fumarsyre-halv-esterne fremstilles ved å la reagere i det vesentlige like molmengder av maleinsyreanhydrid og en enverdig alkohol med en temperatur av fra ca. 20 til ca. 200°C og maleinsyre-halv-esteren isomeriseres til fumarsyre-halv-esteren under anvendelse av varme og/ eller en isomeriseringskatalysator. The fumaric acid half-esters are produced by reacting substantially equal molar amounts of maleic anhydride and a monohydric alcohol at a temperature of from approx. 20 to approx. 200°C and the maleic acid half-ester is isomerized to the fumaric acid half-ester using heat and/or an isomerization catalyst.
Ved utførelsen av forestringen med maleinsyreanhydrid kan det anvendes forskjellige forestringskatalysatorer, som f. eks. BF3, p-toluen-sulfonsyre osv. for å katalysere dannelsen av maleinsyre-halv-esteren. Imidlertid er det å foretrekke å unngå anvendelsen av disse katalysatorer, da de forhindrer den viktige dannelse av halv-estere ved at de også innvirker på reaksjonen av den frie syregruppe i halv-esteren med hydroxyforbndelsen, hvorved utbyttet av diester og dicarboxylsyre økes. Følgelig inneholder forestrings-reaksjonsproduktet fra maleinsyreanhydrid en blanding av diester, monoester, dicarboxylsyre (både maleinsyre og fumarsyre) og muligens noe ureagert anhydrid. When carrying out the esterification with maleic anhydride, different esterification catalysts can be used, such as e.g. BF3, p-toluenesulfonic acid, etc., to catalyze the formation of the maleic half-ester. However, it is preferable to avoid the use of these catalysts, as they prevent the important formation of half-esters by also affecting the reaction of the free acid group in the half-ester with the hydroxy compound, whereby the yield of diester and dicarboxylic acid is increased. Consequently, the esterification reaction product from maleic anhydride contains a mixture of diester, monoester, dicarboxylic acid (both maleic and fumaric acid) and possibly some unreacted anhydride.
Tilstedeværelsen av en ureaktiv maleinsyre-ester kan tolereres da det bare øker omkostningene til sluttproduktet. Fri maleinsyreanhydrid eller fri dicarboxylsyre, i reaksjonsblandingen forårsaker imidlertid et alvorlig problem, da disse forbindelser kan fornette eller kryssbinde for tidlig materialer som har mer enn en ethylenisk umettet gruppe pr. molekyl, til en usmeltbar masse. (Når det bare er en ethylenisk umettet gruppe pr. molekyl, så forårsaker ikke fri maleinsyreanhydrid eller dicarboxylsyre noe problem. Videre er fumarsyre som også er til stede, så inert og uoppløselig og har et slikt høyt smel-tepunkt at det ofte utfelles fra det monomere reaksjonsprodukt og/eller de ferdige polymer-masser som fremstilles fra det.) Når en poly-umettet forbindelse reageres med halv-esteren, kan følgelig fri dicarboxylsyre eller anhydrid i haJv-esterreaksjonsproduktet tolereres bare i meget små mengder, hvor det er ønskelig å holde mengden pa et minimum. Når en forestringskatalysator av den ovennevnte type anvendes ved fremstillingen av halv-esteren, er det der-for å foretrekke å anvende et overskudd av monohydroxyforbindelsen og/eller å fraskille halv-esteren fra et anhydrid eller en dicarboxylsyre som dannes under forestringen. The presence of an unreactive maleic acid ester can be tolerated as it only increases the cost of the final product. Free maleic anhydride or free dicarboxylic acid, in the reaction mixture, however, causes a serious problem, as these compounds can cross-link or cross-link prematurely materials having more than one ethylenically unsaturated group per molecule, into an infusible mass. (When there is only one ethylenically unsaturated group per molecule, free maleic anhydride or dicarboxylic acid causes no problem. Furthermore, fumaric acid, which is also present, is so inert and insoluble and has such a high melting point that it often precipitates from the monomeric reaction product and/or the finished polymer masses produced from it.) When a polyunsaturated compound is reacted with the half-ester, consequently free dicarboxylic acid or anhydride in the haJv-ester reaction product can be tolerated only in very small amounts, where it is desirable to keep the amount to a minimum. When an esterification catalyst of the above type is used in the preparation of the half-ester, it is preferable to use an excess of the monohydroxy compound and/or to separate the half-ester from an anhydride or a dicarboxylic acid which is formed during the esterification.
Halv-esteren kan fremstilles direkte fra cis-eller trans-dicarboxylsyren eller syrehalogeni-det, og i dette tilfelle anvendes fordelaktig de ovennevnte forestringskatalysatorer. Også i dette tilfelle vil vanligvis forestringsreaksjons-produktet inneholde en blanding av alle forbindelsene som kan forekomme med maleinsyrean-hydridet, og man må være oppmerksom på en forestringskatalysator og de samme forsiktig-hetsregler. The half-ester can be prepared directly from the cis- or trans-dicarboxylic acid or the acid halide, and in this case the above-mentioned esterification catalysts are advantageously used. Also in this case, the esterification reaction product will usually contain a mixture of all the compounds that can occur with the maleic anhydride, and one must be aware of an esterification catalyst and the same precautions.
Av de foregående årsaker og fordi det innledende reaksjonsprodukt av ekvimolare mengder av anhydrid og monohydroxyforbindelsen ved fravær av en katalysator er harvesteren i nesten kvantitativt utbytte, er dette den foretrukkede arbeidsmåte. For the foregoing reasons and because the initial reaction product of equimolar amounts of the anhydride and the monohydroxy compound in the absence of a catalyst is the harvester in near quantitative yield, this is the preferred mode of operation.
Skjønt monohydroxyforbindelsen og malein-syreannydrid fortrinsvis anvendes, i det vesentlige i like moldeler, er det mulig å anvende en av forbindelsene i overskudd. Når imidert&d maleinsyreanhydrid anvendes i et molart overskudd av 25 pst. eller mer like overfor monohydroxyforbindelsen (dvs. et forhold av mer enn 1,0 til 0,8), må halv-esteren isoleres fra reaksjonsblandingen før den bringes til å reagere med en polymettet forbindelse, da dicarboxylsyre som dannes i det ureagerte anhydrid, kan fornette seg med den polyumettede forbindelse til en usmeltbar masse, slik som tidligere nevnt. På den annen side kan alkoholer anvendes i et vesentlig overskudd (f. eks. 3 eller 4 mol på hvert mol anhydrid) forutsatt at det ikke er tilstede noen forestringskatalysator. Den frie, overskytende alkohol må imidlertid fjernes før halogenaeyleringen, da den ellers vil konkur-rere med syreacrylforbindelsen ved reaksjon med carboniumionet og herved nedsettes utbyttet av acryloxyhalogengruppene. Når en forestringskatalysator er til stede, skal molforholdet av alkohol til anhydrid være høyere enn 1,5 til 1. Aromatiske hydroxyforbindelser som f. eks. fenol eller cresol, skal anvendes i et overskudd hvis ikke den ureagerte hydroxyforbindelse er fjernet, da eventuelt ureagerte deler av disse aromatiske hydroxyforbindelser kan hemme den påfølgende sampolymerisering av deres monomere halogenacyleringsreaksjonsprodukter. Although the monohydroxy compound and maleic anhydride are preferably used, essentially in equal parts, it is possible to use one of the compounds in excess. When imidated maleic anhydride is used in a molar excess of 25 percent or more equal to the monohydroxy compound (ie, a ratio of more than 1.0 to 0.8), the half-ester must be isolated from the reaction mixture before it is reacted with a polysaturated compound, as the dicarboxylic acid formed in the unreacted anhydride can crosslink with the polyunsaturated compound to an infusible mass, as previously mentioned. On the other hand, alcohols can be used in substantial excess (eg 3 or 4 moles for each mole of anhydride) provided no esterification catalyst is present. The free, excess alcohol must, however, be removed before the halogenaylation, as otherwise it will compete with the acid acrylic compound by reaction with the carbonium ion and thereby reduce the yield of the acryloxyhalogen groups. When an esterification catalyst is present, the molar ratio of alcohol to anhydride should be higher than 1.5 to 1. Aromatic hydroxy compounds such as phenol or cresol, must be used in excess if the unreacted hydroxy compound has not been removed, as any unreacted parts of these aromatic hydroxy compounds can inhibit the subsequent copolymerization of their monomeric halogen acylation reaction products.
Halv-esterne kan fremstilles ved en temperatur av fra ca. 20 til ca. 200°C. Imidlertid er det vanligvis, å foretrekke å utføre denne reaksjon ved moderat forhøyet temperatur (f. eks. 80 til 150°C) for å oppnå en hurtig reaksjon uten at halv-esteren utsettes for dismutasjon (dvs. dannelse av diester og dicarboxylsyrer. Etter som reaksjonen øker, øker også muligheten for dismutasjon. The half-esters can be produced at a temperature of from approx. 20 to approx. 200°C. However, it is usually preferable to carry out this reaction at a moderately elevated temperature (eg 80 to 150°C) to achieve a rapid reaction without subjecting the half-ester to dismutation (ie formation of diesters and dicarboxylic acids. After as the reaction increases, so does the possibility of dismutation.
Selv om maleinsyrehalv-esterne kan isomeriseres til fumarsyre-halv-esteren ganske enkelt ved opphetning til en temperatur fra ca. 150 til 220°C, så er det å foretrekke å isomerisere ved lavere temperaturer under anvendelse av en isomeriseringskatalysator. Ved ca. 150°C eller mindre uten katalysatorer er reaksjonen for langsom til å kunne anvendes i praksis, men ved ca. 180°C foreligger det en tendens til at halv-esteren utsettes for dismutasjon, selv i fravær av en ester-utvekslingskatalysator, så at det dannes fri dicarboxylsyre. For å unngå dette problem anvendes en isomeriseringskatalysator og med en slik katalysator kan halvesteren til maleinsyre hurtig omdannes til halv-esteren av fumarsyre ved en temperatur av fra 50 til 150°C uten noen nevneverdig dismutasjon. Ved temperaturer så lave som 80 til 110°C er isomeriseringen fullstendig fra ca. 5 til 60 minutter. Although the maleic acid half-esters can be isomerized to the fumaric acid half-ester simply by heating to a temperature from about 150 to 220°C, then it is preferable to isomerize at lower temperatures using an isomerization catalyst. At approx. 150°C or less without catalysts, the reaction is too slow to be used in practice, but at approx. At 180°C, there is a tendency for the half-ester to undergo dismutation, even in the absence of an ester-exchange catalyst, so that free dicarboxylic acid is formed. To avoid this problem, an isomerization catalyst is used and with such a catalyst the half-ester of maleic acid can be quickly converted to the half-ester of fumaric acid at a temperature of from 50 to 150°C without any significant dismutation. At temperatures as low as 80 to 110°C, the isomerization is complete from ca. 5 to 60 minutes.
De følgende forbindelser kan anvendes som isomeriseringskatalysatorer: fosforoxyklorid, fosfortriklorid, thionylklorid, fosforoxybromid, fosforoxyjodid, fosforoxyfluorid, fosfortribromid, fosfortrijodid, fosfortrifluorid, 2-ethylhexylfos-f ordiklorid, di- (2-ethylhexyl) -f osforyl-mono-klorid, fosforthiobromid, fosforthioklorid, thio-nylbromid, thionylfluorid, hexadecansulfonklor-id, toluensulfonklorid, klorsulfonsyre, svovelmo-nobromid, svovelmonoklorid, svoveldiklorid, sul-furylklorid, jodin, bromin, aluminiumklorid, di-ethylamin, svoveldioxyd, sinkhydrosulfit osv. Disse katalysatorer kan anvendes i en mengde svarende til fra 0,0001 mol til 0,1 mol pr. mol av halv-esteren. Større konsentrasjoner øker bare omkostningene for fremstilling av produktet uten at reaksjonen går lettere .Thionylklorid, aluminiumklorid, fosfortriklorid og fosforoxyklorid er de foretrakkede katalysatorer på grunn av deres lette tilgjengelighet og effektivitet. Når det er ønskelig, er det mulig å isomerisere maleatgrupper til fumaratgrupper etter halogenacyleringsreaksjonen. I disse tilfeller anvendes varme og/eller isomeriseringskatalysatorer på samme måte som når halv-esteren isomeriseres, med den unntagelse at den anvendte The following compounds can be used as isomerization catalysts: phosphorus oxychloride, phosphorus trichloride, thionyl chloride, phosphorus oxybromide, phosphorus oxyiodide, phosphorus oxyfluoride, phosphorus tribromide, phosphorus triiodide, phosphorus trifluoride, 2-ethylhexylphosphorus chloride, di-(2-ethylhexyl)-phosphoryl monochloride, phosphorus thiobromide, phosphorus thiochloride, thionyl bromide, thionyl fluoride, hexadecane sulfon chloride, toluene sulfon chloride, chlorosulfonic acid, sulfur monobromide, sulfur monochloride, sulfur dichloride, sulfuryl chloride, iodine, bromine, aluminum chloride, diethylamine, sulfur dioxide, zinc hydrosulfite, etc. These catalysts can be used in a quantity corresponding to from 0.0001 mol to 0.1 mol per moles of the half-ester. Higher concentrations only increase the cost of producing the product without making the reaction easier. Thionyl chloride, aluminum chloride, phosphorus trichloride and phosphorus oxychloride are the preferred catalysts because of their easy availability and effectiveness. When desired, it is possible to isomerize maleate groups to fumarate groups after the halogenacylation reaction. In these cases, heat and/or isomerization catalysts are used in the same way as when the half-ester is isomerized, with the exception that the used
temperatur bare behøver å være mindre enn temperature only needs to be less than
spaltningstemperaturen for reaksjonsproduktet. Vanligvis er det imidlertid å foretrekke å isomerisere før halogenacyleringsreaksjonen, da av en eller annen ukjent grunn vil monomerer fremstilt på denne måte sampolymerisere med vinylidenforbindelser så at det dannes produkter med høyere strekkstyrke enn tilsvarende sampolymeriseringsprodukter av monomerer som isomeriseres etter halogenacylering. the decomposition temperature of the reaction product. Generally, however, it is preferable to isomerize before the halogenacylation reaction, as for some unknown reason monomers prepared in this way will copolymerize with vinylidene compounds so that products with higher tensile strength are formed than corresponding copolymerization products of monomers which are isomerized after halogenacylation.
Temperatur og eventuell katalysator halogenacyleringsreaksjonen. Temperature and any catalyst the halogen acylation reaction.
Nabo-acyloxyhalogenforbindelser i henhold til oppfinnelsen fremstilles ved å bringe til reaksjon syreacrylforbindelsen, en langkjedet ethylenisk umettet forbindelse og alkylhypohalogenit ved en temperatur av fra ca. —50 til ca. 150°C. Reaksjonen er sterkt eksotherm og reaksjonsblandingen, særlig i støkiometrisk måle-stokk, skai avkjøles for å hindre en ødeleggende temperaturøkning. Nyttige reaksjonshastigheter uten noen skadelig misfarvning av produktet og uten, spaltning oppnås i området 0 til 100°C og det foretrakkede område er ca. 25 til 75°C. Ved 25 til 75°C er reaksjonen i alt vesentlig fullstendig i løpet av 1 til 5 timer, og damptrykket til det foretrakkede hypohalogenit (tertiært butylhypoklorit) er moderat, og produktmisfarvnin-gen er null, og sidereaksjoner mellom syreacrylforbindelsen og det tertiære alkylhyproklorit un-dertrykkes. Høyere reaksjonstemperaturer fører til produktmisfarvning og til problemer som skyldes det høyere damptrykk av hypoklorit og som nødvendiggjør bruken av trykkar. Hoved-ulempen ved lavere temperaturer er en redusert reaksjonshastighet og en tilsvarende lang reak-sjonstid. I det foretrakkede temperaturområde fås nyttige produkter i løpet av 1/4 til 8 timer. Over det bredere temperaturområde av —50 til 150°C vil reaksjontiden vare fra praktisk talt en øyeblikkelig reaksjon til reaksjoner av flere ukers varighet. Adjacent acyloxyhalogen compounds according to the invention are prepared by reacting the acid acrylic compound, a long-chain ethylenic unsaturated compound and alkyl hypohalogenite at a temperature of from approx. -50 to approx. 150°C. The reaction is strongly exothermic and the reaction mixture, especially in stoichiometric measuring scale, must be cooled to prevent a destructive increase in temperature. Useful reaction rates without any harmful discoloration of the product and without decomposition are achieved in the range 0 to 100°C and the preferred range is approx. 25 to 75°C. At 25 to 75°C, the reaction is substantially complete within 1 to 5 hours, and the vapor pressure of the preferred hypohalite (tertiary butyl hypochlorite) is moderate, and product discoloration is zero, and side reactions between the acrylic acid compound and the tertiary alkyl hypochlorite are un- pressed. Higher reaction temperatures lead to product discoloration and to problems due to the higher vapor pressure of hypochlorite and which necessitate the use of pressure vessels. The main disadvantage at lower temperatures is a reduced reaction rate and a correspondingly long reaction time. In the preferred temperature range, useful products are obtained within 1/4 to 8 hours. Over the wider temperature range of -50 to 150°C, the reaction time will range from a practically instantaneous reaction to reactions lasting several weeks.
Når lave temperaturer anvendes eller når When low temperatures are used or when
det ønskes en hurtigere reaksjon, kan det generelt anvendes en katalysator som f. eks. tetra-alkyl-ammoniumsalt eller et tetraalkyl-fosfor-niumsalt. Generelt kan disse katalysatorer anvendes i en konsentrasjon av 0,0001 til 0,1 mol pr. ekvivalent av ethylenisk umettethet i den ethylenisk umettede forbindelse. Tetramethylammoniumklorid er særlig effektivt. if a faster reaction is desired, a catalyst can generally be used, e.g. tetraalkylammonium salt or a tetraalkylphosphonium salt. In general, these catalysts can be used in a concentration of 0.0001 to 0.1 mol per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound. Tetramethylammonium chloride is particularly effective.
Mengdeforhold ved halogenacyleringsreaksjonen Quantity ratio in the halogen acylation reaction
Syreacrylforbindelsen, alkylhypohalogenit og den langkjedete ethylenisk umettede forbin- | deise kan være til stede i reaksjonsblandingen i praktisk talt hvilket som helst forhold. Imidlertid foretrekkes det å, anvende ca. 1 mol alkylhypohalogenit for hver ekvivalent av ethylenisk umettethet i den ethylenisk umettede forbindelse. En høyere mengde av alkylhypohalogenit påskynner reaksjonen bare lite og kan medføre den ulempe at man må fjerne overskudd av hypohalogenit og/eller alkoholiske biprodukter fra reaksjonsproduktet. Denne ulempe kan imidlertid kompenseres ved at sampolymerene i reaksjonsproduktet har en økt seighet og/eller stiv-het. Sampolymerer av styren med reaksjonsproduktet av tertiært butylhypoklorit, sojabønne-olje og acrylsyre i et forhold av 1,20 : 1,00 : 1,35 er f. eks. sterkere og mer stive enn når forholdet er 1,00 : 1,00 : 1,35. En lavere mengde av alkylhypohalogenit reduserer naturligvis antallet av ethyleniske grupper som halogenacyleres. Nyttige produkter fåes imidlertid over området av ca. 0,1 til ca. 3 mol alkylhypohalogenit pr. ekvivalent av ethylenisk umettethet. The acid acrylic compound, alkyl hypohalogenite and the long-chain ethylenically unsaturated compound these may be present in the reaction mixture in virtually any ratio. However, it is preferred to use approx. 1 mole of alkyl hypohalide for each equivalent of ethylenic unsaturation in the ethylenically unsaturated compound. A higher amount of alkyl hypohalogenite accelerates the reaction only slightly and may entail the disadvantage that excess hypohalogenite and/or alcoholic by-products must be removed from the reaction product. However, this disadvantage can be compensated by the fact that the copolymers in the reaction product have an increased toughness and/or stiffness. Copolymers of styrene with the reaction product of tertiary butyl hypochlorite, soybean oil and acrylic acid in a ratio of 1.20 : 1.00 : 1.35 are e.g. stronger and more rigid than when the ratio is 1.00 : 1.00 : 1.35. A lower amount of alkyl hypohalogenite naturally reduces the number of ethylenic groups that are haloacylated. However, useful products are obtained over the area of approx. 0.1 to approx. 3 mol alkyl hypohalogenite per equivalent of ethylenic unsaturation.
Når det er ønskelig å halogenacylere så When it is desirable to haloacylate so
mange som mulig av de ethyleniske dobbeltbindinger i den ethylenisk umettede forbindelse, skal syreacrylforbindelsen anvendes i det foretrakkede forhold av ca. 1,2 til 2 mol pr. ekvivalent av ethylenisk. umettethet i den ethyleniske umettede forbindelse, og den mest effektive konsentrasjon varierer med temperaturen. Ved as many as possible of the ethylenic double bonds in the ethylenically unsaturated compound, the acid acrylic compound must be used in the preferred ratio of approx. 1.2 to 2 moles per equivalent of ethylenic. unsaturation in the ethylenic unsaturated compound, and the most effective concentration varies with temperature. By
f. eks. 45°C er et forhold av 1,7 til 1 mest effektivt, mens ved ca. 65°C er et forhold av 1,35 til 1 mest effektivt. Sammenlignet med resultatene ved et 1 til 1 forhold tilveiebringer de foretrakkede forhold en tydelig høyere reaksjonshastighet og et høyere utbytte av acryloxy-halo-genforbindelsen. Høyere forhold enn 2 tii 1 med-fører en relativ liten ytterligere økning av reak-sjonshastigheten og produktutbytte, og dette er mer enn opphevet ved den ulempe at det må fjernes e n større mengde av ureagert syreacrylforbindelse fra reaksjonsblandingen eller ved de økte omkostninger uten noen tilsvarende fordel, når den ureagerte syreacrylforbindelse blir tilbake i komposisjonen. Nyttige produkter fåes imidlertid over området av fra ca. 0,1 til ca. e.g. 45°C a ratio of 1.7 to 1 is most effective, while at approx. 65°C a ratio of 1.35 to 1 is most effective. Compared to the results at a 1 to 1 ratio, the preferred ratios provide a distinctly higher reaction rate and a higher yield of the acryloxy-halogen compound. Higher ratios than 2 tii 1 lead to a relatively small further increase in the reaction rate and product yield, and this is more than offset by the disadvantage that a larger amount of unreacted acid acrylic compound must be removed from the reaction mixture or by the increased costs without any corresponding advantage, when the unreacted acid acrylic compound remains in the composition. However, useful products are obtained over the area of from approx. 0.1 to approx.
10 mol av syreacrylforbindelsen pr. ekvivalent av ethylenisk umettethet i den ethylenisk umettede 10 mol of the acid acrylic compound per equivalent of ethylenic unsaturation in the ethylenically unsaturated
forbindelse. Skjønt det ikke er av essentiell betydning at den gjenværende syreacrylforbindelse fjernes fra reaksjonsblandingen kan den fjernes sammen med de alkoholiske biprodukter ved alkalisk vandig vaskning eller ved vakuumdestillasjon. connection. Although it is not of essential importance that the remaining acid acrylic compound is removed from the reaction mixture, it can be removed together with the alcoholic by-products by alkaline aqueous washing or by vacuum distillation.
En polymeriseringsinhibitor, som f. eks. me-tallisk kopper, et amin, en fenol- eller kinoidfor-bindelse, skal være til stede ved halogenaeyleringen i en mengde av fra ca. 0,001 til 0,5 vektprosent av de reagerende stoffer når en syreacrylforbindelse som har en ende-ethylenisk umettethet anvendes som acyleringsmiddel. Fortrinnsvis skal inhibitoren anvendes i en mengde av fra 0,01 til 0,1 vektprosent av de reagerende stoffer. Generelt foretrekkes de fenoliske forbindelser, da disse har en mindre tendens til å gi en uønsket farve enn aminene, og aminene har også en tendens til å reagere med alkylhypo-halogenitene. Videre er den tilstrekkelige fenoliske inhibitor vanligvis til stede i de kommer-sielt tilgjengelige monocarboxylsyrer, og i dette tilfelle er det ikke nødvendig å tilsette ytterligere inhibitorer, Syreacrylforbindelser med en forestret carboxylgruppe på {3-carbonatomet (f. eks. maleinsyre-halv-esterne og fumarsyre-halv-esterne) krever ikke tilstedeværelsen av en polymeriseringsinhibitor med mindre det er en ende-umettethet i ett av de reagerende stoffer. A polymerization inhibitor, such as metallic copper, an amine, a phenolic or quinoid compound, must be present during the halogenation in an amount of from approx. 0.001 to 0.5 percent by weight of the reactants when an acid acrylic compound having a terminal ethylenic unsaturation is used as the acylating agent. Preferably, the inhibitor should be used in an amount of from 0.01 to 0.1 percent by weight of the reacting substances. In general, the phenolic compounds are preferred, as these have less of a tendency to give an undesirable color than the amines, and the amines also have a tendency to react with the alkyl hypohalides. Furthermore, the sufficient phenolic inhibitor is usually present in the commercially available monocarboxylic acids, and in this case it is not necessary to add additional inhibitors. and the fumaric acid half-esters) do not require the presence of a polymerization inhibitor unless there is a terminal unsaturation in one of the reactants.
ANVENDELSE APPLICATION
De fysikalske og kjemiske egenskaper av de nye naboacryloxy-halogenforbindelsesreaksj ons-produkter som fremstilles ved denne oppfinnelse, og mer spesielt polymerene og harpiksproduk-tene som fremstilles av disse, kan varieres på mange forskjellige måter ved hensiktsmessig valg av de reagerende stoffer, dvs. den umettede forbindelse og syreacrylforbindelsen og acyle-ringsgraden. Reaksjonsproduktene som fåes ved denne oppfinnelse, kan polymeriseres over ethy-lengrupperie i acyleringssyren med kjente katalysatorer, enten ioniske eller frie radikalkata-lysatorer, så at det dannes nyttige homopolymerer, eller de kan polymeriseres med andre The physical and chemical properties of the new neighboring acryloxy-halogen compound reaction products produced by this invention, and more particularly the polymers and resin products produced from these, can be varied in many different ways by appropriate selection of the reacting substances, i.e. the unsaturated compound and the acid acrylic compound and the degree of acylation. The reaction products obtained by this invention can be polymerized over the ethylene group in the acylating acid with known catalysts, either ionic or free radical catalysts, so that useful homopolymers are formed, or they can be polymerized with other
vinylidenforbindelser så at det dannes nyttige vinylidene compounds so that useful is formed
sampolymerer. Blant de andre vinylidenmono-merer, med hvilke acryloxy-halogenforbindelse-reaksjonsproduktene i henhold til oppfinnelsen kan sampolymeriseres, er methylmethacrylat, copolymers. Among the other vinylidene monomers, with which the acryloxy-halogen compound reaction products according to the invention can be copolymerized, are methyl methacrylate,
ethylacrylat, butylmethacrylat, stearylacrylat, ethyl acrylate, butyl methacrylate, stearyl acrylate,
acrylsyre, methacrylsyre, styren, a-methylstyren, allyl-alkohol, vinylacetat, vinylstearat, vinylklorid, vinylidenklorid, acrylamid, acrylnitril, buta-dien osv. Acryloxyhalogenproduktene i henhold til oppfinnelsen kan sampolymeriseres med et stort antall forskjellige monomerer med indre ethylenisk umettethet under anvendelse av van-lige katalysatorer og polymeriseringsforhold, så at man får nyttige sampolymerer. Blant slike forbindelser er maleinsyreanhydrid, crotonsyre, kanelsyre, dipenten, myrcen osv. Sampolymerene som fremstilles på denne måten, varierer fra viskose væsker til bløte geler og til seige gummi-aktige produkter og harde harpikser. Polymerene acrylic acid, methacrylic acid, styrene, α-methylstyrene, allyl alcohol, vinyl acetate, vinyl stearate, vinyl chloride, vinylidene chloride, acrylamide, acrylonitrile, butadiene, etc. The acryloxyhalogen products according to the invention can be copolymerized with a large number of different monomers with internal ethylenic unsaturation during use of common catalysts and polymerization conditions, so that useful copolymers are obtained. Among such compounds are maleic anhydride, crotonic acid, cinnamic acid, dipentene, myrcene, etc. The copolymers produced in this way vary from viscous liquids to soft gels and to tough gummy products and hard resins. The polymers
(dvs. homopolymerene og sampolymerene) er generelt nyttige ved fremstillingen av støpte, for- (i.e. the homopolymers and copolymers) are generally useful in the manufacture of molded, pre-
mete og ekstruderte produkter, som fiber-for-sterkede laminerings-harpikser og formnings-harpikser, som overflatebelegg, klebemidler, plastiseringsmidler og som papir- og tekstilbe-handlingsmidler. met and extruded products, such as fiber-reinforced laminating resins and molding resins, as surface coatings, adhesives, plasticizers and as paper and textile treatment agents.
Produktene i henhold til oppfinnelsen er nyttige for fremstilling av homopolymerer og sampolymerer. Methacryloxy- og acryloxyforbin-delser er fotofølsomme og må lagres i mørket for å hindre for tidlig polymerisering. Ved fravær av lys er de stabile i måneder ved romtemperatur. For å hindre ødeleggelse på grunn av labilt halogen, bør de lagrete acryloxy-halo-genmonomerer inneholde ca. 0,05 til 5 vektprosent av en stabilisator, som f. eks. en barium - cadmiumsåpe, epoxydisert sojabønneolje eller et tinnmercaptid. Praktisk talt hvilke som helst av de stabiliseringsmidler som anvendes, for polyolefiner fremstillet med en katalysator av Zieglertypen kan innføres i disse produkter, så fremt stabiliseringsmidlet ikke hindrer den på-følgende polymerisering. The products according to the invention are useful for the production of homopolymers and copolymers. Methacryloxy and acryloxy compounds are photosensitive and must be stored in the dark to prevent premature polymerization. In the absence of light, they are stable for months at room temperature. To prevent spoilage due to labile halogen, the stored acryloxy-halogen monomers should contain approx. 0.05 to 5% by weight of a stabilizer, such as e.g. a barium-cadmium soap, epoxidized soybean oil or a tin mercaptide. Practically any of the stabilizers used for polyolefins produced with a catalyst of the Ziegler type can be introduced into these products, as long as the stabilizer does not prevent the subsequent polymerization.
Andre-, variasjoner ved fremgangsmåten Selv om fremgangsmåten først og fremst er rettet på halogenacylering av langkjedete ethylenisk umettede forbindelser, så kan den også anvendes for, å innføre en acryloxygruppe i . et stort antall forskjellige andre ethylenisk umettede forbindelser, som f. eks. ethylen, propylen, buten-1, buten-2, hexen-J, hepten-3, diis<q>buty-len,nonen-3, octadecen-1, butadién, isppren, tetramethylethylen, cyclohexen, cycloocten, al-fa^pinenstyren, alfa-methylstyren, p-methylstyren, o-octylsyren, 2,5-diklorstyren, yinylklorid, vinylbromid, allylklorid, klorpren, allylalkohol, diallyloxypentaerythritol, vinylacetat, vinylpro-pionat, vinylstearat, methylacrylat, stearylme-thacrylat, acrylsyre, methacrylsyre.acrylnitril, acrylamid osv. eller endog naturlig gummi. Som en generell regel kan slike forbindelser som inneholder en indre ethylenisk dobbéltbinding, som f. eks. cyclohexen eller nonen-3, halogenacyleres under de samme forhold som de foretrukkede langkj edete ethylenisk umettede forbindelser i henhold til oppfinnelsen. På den annen side krever slike forbindelser, som inneholder bare en del umettethet, som ethylen og propylen, temperaturer høyere enn. ca. 20°C og/eller en halogenacylerings-katalysator (f. eks. tetramethylammoniumklorid), da ende-ethyleniske dobbeltbindinger er noe vanskeligere å halogenacylere enn indre ethyleniske dobbeltbindinger. Slike forbindelser som vinylklorid og selve acrylsyren er ennå vanskelige å halogenacylere på grunn av tilstedeværelsen av elektrofile grupper i nær forbindelse med den ethyleniske dobbéltbinding. Jo større antallet av elektrofile grupper foreligger i nær tilknytning til den ethyleniske dobbéltbinding, desto vanskeligere er det å halogenacylere den ethyleniske dobbéltbinding; slike stoffer kan bare halogenacyleres ved hjelp av en halogenacyleringskatalysator ved en temperatur høyere enn ca. 20°C. Other variations in the method Although the method is primarily aimed at halogen acylation of long-chain ethylenically unsaturated compounds, it can also be used to introduce an acryloxy group in . a large number of different other ethylenically unsaturated compounds, such as e.g. ethylene, propylene, butene-1, butene-2, hexene-J, heptene-3, diis<q>butylene, nonene-3, octadecene-1, butadiene, ispprene, tetramethylethylene, cyclohexene, cyclooctene, al-fa^ pinenestyrene, alpha-methylstyrene, p-methylstyrene, o-octyl styrene, 2,5-dichlorostyrene, yinyl chloride, vinyl bromide, allyl chloride, chloroprene, allyl alcohol, diallyloxypentaerythritol, vinyl acetate, vinyl propionate, vinyl stearate, methyl acrylate, stearyl methacrylate, acrylic acid, methacrylic acid. acrylonitrile, acrylamide etc. or even natural rubber. As a general rule, such compounds containing an internal ethylenic double bond, such as e.g. cyclohexene or nonene-3, is haloacylated under the same conditions as the preferred long-chain ethylenically unsaturated compounds according to the invention. On the other hand, such compounds, which contain only some unsaturation, such as ethylene and propylene, require temperatures higher than about. 20°C and/or a halogenacylation catalyst (e.g. tetramethylammonium chloride), as terminal ethylenic double bonds are somewhat more difficult to halogenacylate than internal ethylenic double bonds. Such compounds as vinyl chloride and acrylic acid itself are still difficult to halogenacylate because of the presence of electrophilic groups in close connection with the ethylenic double bond. The greater the number of electrophilic groups present in close proximity to the ethylenic double bond, the more difficult it is to halogenacylate the ethylenic double bond; such substances can only be halogenacylated using a halogenacylation catalyst at a temperature higher than approx. 20°C.
Etter som reaktiviteten av den ethyleniske' After as the reactivity of the ethylenic'
umettede forbindelse like overfor halogenacylering avtar, øker tendensen til den ethyleniske dobbéltbinding i den sure acrylforbindelse til å bli halogenacylert og følgelig dannes dette biprodukt i øket mengde i reaksjonsproduktet. Dette reaksjonsprodukt er forlikelig med de forskjellige andre produkter som dannes under halogenaeyleringen og polymerene herav. 'Den halogenacylerte sure acrylforbindelse kan imidlertid ekstraheres med alkali. Som nevnt tidligere er acyleringssyrer som f. eks. kloracrylsyre og halv-esterne av maleinsyre og fumarsyre, mindre utsatt for angrep av alkylhypohalogenit enn selve acrylsyren og methåcrylsyre. Følgelig kan mengden av biprodukter som dannes ved halogenacylering av den åcylerende syre reguleres ved valget av den åcylerende'syre. unsaturated compound opposite to halogen acylation decreases, the tendency of the ethylenic double bond in the acidic acrylic compound to be halogen acylated increases and consequently this by-product is formed in increased quantity in the reaction product. This reaction product is compatible with the various other products formed during halogenation and the polymers thereof. However, the halogenacylated acid acrylic compound can be extracted with alkali. As mentioned earlier, acylating acids such as chloroacrylic acid and the half-esters of maleic acid and fumaric acid, less susceptible to attack by alkyl hypohalogen than acrylic acid and methacrylic acid itself. Accordingly, the amount of by-products formed by haloacylation of the acylating acid can be regulated by the choice of the acylating acid.
Disse forbindelser er bare egnete'og nyttige sampolymeriserbare og/eller homopolymeriser-bare monomerer. Produktene basert på ethylen og propylen er særlig av interesse, da disse halo-genalkylestere av en syreacrylforbindelse lett kan omdannes til tilsvarende aminoalkylestere og/eller umettede estere med umettethet i både esterens alkoholdel og syredel. These compounds are only suitable and useful copolymerizable and/or homopolymerizable monomers. The products based on ethylene and propylene are of particular interest, as these haloalkyl esters of an acid acrylic compound can easily be converted into corresponding aminoalkyl esters and/or unsaturated esters with unsaturation in both the alcohol part and the acid part of the ester.
De følgende eksempler skal tjene til å klar-gjøre oppfinnelsen. I eksemplene betyr «mekv.» milliekvivalenter. The following examples shall serve to clarify the invention. In the examples, "mekv" means milliequivalents.
Eksempel 1. Example 1.
174 g (2 mol) methåcrylsyre som inneholdt 0,025 vektprosent p-methoxyfenol og 204 g soja-bønneolje (1,00 ekvivalent av ethylenisk umetthet) ble innveiet i en Mbrton-kolbe utstyrt med en rører, termometer, tilbakeløpskondensator og dryppetrakt med et innløpsrør som var ført ned til bunnen av kolben. 112 g 97 psts. rent tertiært butylhypoklorit (1,0 mol) ble tilsatt gradvis fra dryppetrakten. over en 15 minutters pe-riode til den omrørte reaksjonsblanding mens den ble avkjølt for å holde temperaturen'ved 40°C. Omrøringen ved samme temperatur méd opphetning etter som det var nødvendig, ble fortsatt i 5 timer. En liten prøve av produktet, som veiet 490 g ble tatt til side for å analyseres! Reaksjonsblandingen ble fortynnet med et like volum hexan og gjentagne ganger vasket med 50.ml's deler av 10 psts. vandig dinatriumfosfat 174 g (2 moles) of methacrylic acid containing 0.025 weight percent p-methoxyphenol and 204 g of soybean oil (1.00 equivalent of ethylenic unsaturation) were weighed into a Mbrton flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel with an inlet tube which had been led down to the bottom of the flask. 112 g 97 percent. pure tertiary butyl hypochlorite (1.0 mol) was added gradually from the dropping funnel. over a 15 minute period to the stirred reaction mixture while it was cooled to maintain the temperature at 40°C. Stirring at the same temperature with heating as necessary was continued for 5 hours. A small sample of the product, which weighed 490 g, was taken aside to be analyzed! The reaction mixture was diluted with an equal volume of hexane and repeatedly washed with 50 ml portions of 10 psts. aqueous disodium phosphate
inntil en prøve vasket med destillert varih'-ikke viste noen gjenværende fri syre. Den alkaliske vaskriing fjernet, også biproduktet 'tertiært butylalkohol fra hexanoppløsningen av reaksjonsproduktet. Hexanet ble derpå vakuumutdrevet og man fikk 312 g av en klår, lysegul olje. until a sample washed with distilled varih'-did not show any residual free acid. The alkaline wash also removed the by-product tertiary butyl alcohol from the hexane solution of the reaction product. The hexane was then evacuated under vacuum and 312 g of a clear, pale yellow oil was obtained.
Produktene som er merket A, det ubehand-lete reaksjonsprodukt, og C, det alkalivaskete produkt ble analysert på vinylumettethet, total umettethet, klor og surhet. Total endeumet-tethet ble bestemt ved en nær infrarød absorp-sjonsbåndmetode (NIR) som beskrevet av R. F. Goddur på side 1790 i bind 29 i «Analytical Che-mistry». Den totale ethyleniske umettethet ble bestemt ved hjelp av pyridinsulfatdibromid-me-toden som er beskrevet på side 203 i 1954-utgaven av «Monomeric Acrylic Esters» av E. H. Riddle. The products labeled A, the untreated reaction product, and C, the alkali-washed product, were analyzed for vinyl unsaturation, total unsaturation, chlorine and acidity. Total endumene density was determined by a near infrared absorption band (NIR) method as described by R. F. Goddur on page 1790 in volume 29 of Analytical Chemistry. The total ethylenic unsaturation was determined by the pyridine sulfate dibromide method described on page 203 of the 1954 edition of "Monomeric Acrylic Esters" by E. H. Riddle.
Av de ovenfor anførte dataer ble det bereg-net at 65,2 molprosent av de ethyleniske dobbeltbindinger i sojabønneolje nå var substituert med nabo-methacryloxy- og klorgrupper, 15 molprosent av de ethyleniske dobbeltbindinger i sojabønneoljen var allylkloridgrupper og at 19,8 molprosent av de ethyleniske dobbeltbindinger i sojabønneoljen nu var substituert med nabo-butoxy- og klorgrupper. From the above data, it was calculated that 65.2 mole percent of the ethylenic double bonds in soybean oil were now substituted with neighboring methacryloxy and chlorine groups, 15 mole percent of the ethylenic double bonds in soybean oil were allyl chloride groups and that 19.8 mole percent of the ethylenic double bonds in the soybean oil were now substituted with neighboring butoxy and chlorine groups.
Eksempel 2. Example 2.
Eksempel 1 ble gjéntatt med unntagelse av at 1,7 mol methåcrylsyre ble anvendt i stedenfor 2,0 mol og reaksjonen ble utført i 2 timer i stedenfor i 5 timer. Før den alkaliske ekstraksjon ble utført ble prøven vakuumdestillert ved 25 mm trykk og 50°C for å fjerne den tertiære butylalkohol og en del av den ureagerte methåcrylsyre. Denne' prøve er merket produkt B. Example 1 was repeated with the exception that 1.7 mol of methacrylic acid was used instead of 2.0 mol and the reaction was carried out for 2 hours instead of 5 hours. Before the alkaline extraction was carried out, the sample was vacuum distilled at 25 mm pressure and 50°C to remove the tertiary butyl alcohol and part of the unreacted methacrylic acid. This sample is labeled product B.
Av de ovenfor anførte dataer ble det bereg-net at 72,2 molprosent av ethyleniske dobbeltbindinger i sojabønneoljen hadde nabo-methacryloxy- og klorsubstituenter, 8,8 molprosent av de ethyleniske dobbeltbindinger i sojabønne-oljen var allylkloridgrupper og at 19 molprosent av de ethyleniske dobbeltbindinger i sojabønne-oljen hadde nabo-butoxy- og klorsubstituenter. From the above data, it was calculated that 72.2 mole percent of ethylenic double bonds in the soybean oil had neighboring methacryloxy and chlorine substituents, 8.8 mole percent of the ethylenic double bonds in the soybean oil were allyl chloride groups and that 19 mole percent of the ethylenic double bonds in the soybean oil had neighboring butoxy and chlorine substituents.
Eksempel 3. Example 3.
Eksempel 1 ble gjentatt med unntagelse av at acrylsyren ble anvendt i stedenfor methåcrylsyre. 61,9 molprosent av de ethyleniske dobbeltbindinger i sojabønneoljen hadde nabo-acryloxy-og klorgrupper. Example 1 was repeated with the exception that acrylic acid was used instead of methacrylic acid. 61.9 mole percent of the ethylenic double bonds in the soybean oil had neighboring acryloxy and chlorine groups.
Eksempel 4. Example 4.
Eksempel 2 ble gjentatt bortsett fra at acrylsyren ble anvendt i stedenfor methåcrylsyre og reaksjonen ble utført ved 65°C i 1,5 timer. 59,7 molprosent av de ethyleniske dobbeltbindinger i sojabønneoljen ble substituert med nabo-acryloxy- og klorgrupper. Example 2 was repeated except that acrylic acid was used instead of methacrylic acid and the reaction was carried out at 65°C for 1.5 hours. 59.7 mole percent of the ethylenic double bonds in the soybean oil were substituted with neighboring acryloxy and chlorine groups.
Eksempel 5. Example 5.
96,4 g acrylsyre (1,32 mol) som inneholdt 0,02 vektprosent p-methoxyfenol og 300 g soja-bønneolje (1,50 ekvivalenter ethylenisk umettethet) ble innveiet i en Morton-kolbe forsynt med utstyr som beskrevet i eksempei 1. 168 g 97,5 psts. 96.4 g of acrylic acid (1.32 mol) containing 0.02% by weight of p-methoxyphenol and 300 g of soybean oil (1.50 equivalents of ethylenic unsaturation) were weighed into a Morton flask equipped with equipment as described in Example 1. 168 g 97.5 percent
rent tertiært butylhypoklorit (1,5 mol) ble tilsatt gradvis fra drypptrakten i løpet av 15 minutter til den omrørte blanding, mens reaksjonsblandingen ble avkjølt for å holde temperaturen ved 65—70°C. Omrøringen ved den samme temperatur, opphetning etter som det ble krevet ble fortsatt i 85 minutter. En total mengde av 120 g tertiær butylalkohol og ureagert acrylsyre ble vakuumdestillert ved 50 mm trykk; neat tertiary butyl hypochlorite (1.5 mol) was added gradually from the dropping funnel over 15 minutes to the stirred mixture while the reaction mixture was cooled to maintain the temperature at 65-70°C. Stirring at the same temperature, heating as required, was continued for 85 minutes. A total amount of 120 g of tertiary butyl alcohol and unreacted acrylic acid was vacuum distilled at 50 mm pressure;
De gjenværende 444 g av produktet ble sam-pblymerisert med 30 vektprosent styren under anvendelse av 1 vektprosent benzoyiperoxyd. The remaining 444 g of product was copolymerized with 30% by weight styrene using 1% by weight benzoyl peroxide.
Eksempel 6. Example 6.
Eksempel 5 ble gjentatt med unntagelse av at 1,13 mol acryisyre ble reagert i 65 minutter i stedenfor 1,32 mol acrylsyre. Example 5 was repeated with the exception that 1.13 mol of acrylic acid was reacted for 65 minutes instead of 1.32 mol of acrylic acid.
Eksempel 7. Example 7.
Eksempel 5 ble gjentatt med unntagelse av at 0,99 mol acrylsyre og 1,13 mol tertiært butylhypoklorit ble reagert i 55 minutter i stedenfor 1,32 mol acrylsyre og 1,5. mol tertiært butylhypoklorit. Example 5 was repeated with the exception that 0.99 mol of acrylic acid and 1.13 mol of tertiary butyl hypochlorite were reacted for 55 minutes instead of 1.32 mol of acrylic acid and 1.5. moles of tertiary butyl hypochlorite.
Resultatene av de neste ti eksempler er anført i tabell VI. The results of the next ten examples are listed in Table VI.
Eksempel 8. Example 8.
iy2 mol maleinsyreanhydrid (147 g) ble innveiet i en kolbe utstyrt med en rører, termometer, kondensator og dryppetrakt, og derpå opphetet til 1C5°C. H/2 mot methanol (48 g) ble tilsatt langsomt fra dryppetrakten, mens reaksjonsblandingens temperatur ble holdt ved 90— 100°C. Når det var utviklet tilstrekkelig varme ved reaksjonen ble den ytterligere opphetning avbrutt og temperaturen steg til 135—140°C. Reaksjonsblandingen lot man avkjøle seg til 100°C, og holdt ved denne temperatur i 1 time. En analytisk prøve av reaksjonsproduktet hadde en syreverdi av 7,58 mekv/g "(teoretisk 7,70 mekv/g) og et forsåpningstall av 15,34 mekv/g (teoretisk 15,40 mekv/g). Infrarød spektrofotometrisk- analyse bekreftet at halv-esteren av maleinsyre var blitt fremstilt. 0,68 g PCli, (0,005 mol )ble tilsatt til reaksjonsblandingen, mens reagensene ble holdt ved 110°C i 12 minutter. Infrarød analyse viste av 95 pst. maleinsyre-halv-ester var blitt isomerisert til fumarat-halv-estergrupper. (A) 26 g methylhydrogenfumarat (0,2 mol), 40 g sojabønneolje (0,2 ekvivalent) og 0,01 vektprosent p-methoxyfenol ble opphetet til 65 °C i en Morton-kolbe utstyrt som beskrevet tidligere. iy2 moles of maleic anhydride (147 g) were weighed into a flask equipped with a stirrer, thermometer, condenser and dropping funnel, and then heated to 1C5°C. H/2 to methanol (48 g) was added slowly from the dropping funnel, while the temperature of the reaction mixture was maintained at 90-100°C. When sufficient heat had been developed by the reaction, further heating was stopped and the temperature rose to 135-140°C. The reaction mixture was allowed to cool to 100°C and held at this temperature for 1 hour. An analytical sample of the reaction product had an acid value of 7.58 meq/g (theoretical 7.70 meq/g) and a saponification number of 15.34 meq/g (theoretical 15.40 meq/g). Infrared spectrophotometric analysis confirmed that the half-ester of maleic acid had been prepared. 0.68 g of PCli, (0.005 mol) was added to the reaction mixture, while the reagents were held at 110°C for 12 minutes. Infrared analysis showed that 95% of the maleic half-ester was has been isomerized to fumarate half-ester groups.(A) 26 g methyl hydrogen fumarate (0.2 mol), 40 g soybean oil (0.2 equivalent) and 0.01 wt% p-methoxyphenol were heated to 65 °C in a Morton flask equipped as described previously.
22,5 g tertiært butylhypoklorit (0,2 mol ble gradvis tilsatt til reaksjonsblandingen under av-kjøling for å holde temperaturen ved 65°C. Reaksjonen ble fortsatt ved denne temperatur i 60 minutter. Produktet veiet 110,6 g. 22.5 g of tertiary butyl hypochlorite (0.2 mol) was gradually added to the reaction mixture while cooling to maintain the temperature at 65°C. The reaction was continued at this temperature for 60 minutes. The product weighed 110.6 g.
(B) En annen prøve som veiet 74,6 g, ble fremstilt ved fremgangsmåten i henhold til (A) (B) Another sample weighing 74.6 g was prepared by the method according to (A)
med unntagelse av de flyktige stoffer ble fjernet ved vakuumdestillasjon ved 50 mm trykk. with the exception of the volatile substances were removed by vacuum distillation at 50 mm pressure.
En del av produktet (B) ble blandet med 33 vektprosent styren, 1 pst. Advastab B-C-105 varmestabilisator (en metallsåpe) og 1 pst. ben-oylperoxyd og plasert i en aluminiumveieskål. Ved tildekning med en annen veieplate, ble det dannet en sirkulær form med 5 cm diameter. Polymerisering ved 80°C i 6 timer gav et 0,32 cm tykt polymerstøp. A portion of the product (B) was mixed with 33 weight percent styrene, 1 percent Advastab B-C-105 heat stabilizer (a metal soap), and 1 percent benzoyl peroxide and placed in an aluminum weighing pan. When covered with another weighing plate, a circular shape with a diameter of 5 cm was formed. Polymerization at 80°C for 6 hours gave a 0.32 cm thick polymer cast.
Eksempel 9. Example 9.
Eksempel 8 ble gjentatt med unntagelse av at isomeriseringen ble utelatt. Example 8 was repeated with the exception that the isomerization was omitted.
Eksempel 10. Example 10.
Ethyl-halv-esterproduktet ble fremstilt under anvendelse av fremgangsmåten og molforholdene av reaksjonsmidlene i eksempel 8 med unntagelse av at halv- esteren ble isomerisert ved 80°C i 10 minutter under anvendelse av 0,33 vektprosent thionylklorid. The ethyl half-ester product was prepared using the method and molar ratios of the reactants in Example 8 with the exception that the half-ester was isomerized at 80°C for 10 minutes using 0.33 weight percent thionyl chloride.
Eksempel 11. Example 11.
Eksempel 10 ble gjentatt med unntagelse av at isomeriseringen ble utelatt. Example 10 was repeated with the exception that the isomerization was omitted.
Eksempel 12. Example 12.
Isopropyl-halv-esterproduktet ble fremstilt under anvendelse av fremgangsmåten og molforholdet av reaksjonsmidlene i eksempel 8 med unntagelse av at halv-esteren ble isomerisert ved fra 60—80 °C i 30 minutter under anvendelse av 2,0 vektprosent thionylklorid og halogenaeyleringen ble utført ved 40°C i løpet av 90 minutter. The isopropyl half-ester product was prepared using the procedure and molar ratio of reactants in Example 8 except that the half-ester was isomerized at from 60-80°C for 30 minutes using 2.0% by weight of thionyl chloride and the halogenaylation was carried out at 40°C within 90 minutes.
Eksempel 13. Example 13.
Eksempel 12 ble gjentatt med unntagelse av at isomeriseringen ble utelatt. Example 12 was repeated with the exception that the isomerization was omitted.
Eksempel 14. Example 14.
n-propyl-halv-esterproduktet ble fremstilt under anvendelse av fremgangsmåten og molforholdet av reaksjonsmidlene i eksempel 8 med unntagelse av at halv-esteren ble isomerisert ved 90—100°C i 10 minutter under anvendelse av The n-propyl half-ester product was prepared using the procedure and molar ratio of reactants in Example 8 with the exception that the half-ester was isomerized at 90-100°C for 10 minutes using
1,0 vektprosent thionylklorid, og halogenaeyleringen ble utført ved 55<C>C i løpet av 60 minutter. 1.0% by weight thionyl chloride, and the halogenaylation was carried out at 55<C>C during 60 minutes.
Eksempel 15. Example 15.
Isobutyl-halv-esterproduktet ble fremstilt under anvendelse av fremgangsmåten og molforholdet av reaksjonsmidler i eksempel 8, med unntagelse av at halv-esteren ble isomerisert ved 85°C i 15 minutter under anvendelse av 0,28 vektprosent thionylklorid og halogenaeyleringen ble utført ved 60 °C i løpet av 90 minutter. The isobutyl half-ester product was prepared using the procedure and molar ratio of reactants in Example 8, except that the half-ester was isomerized at 85°C for 15 minutes using 0.28% by weight thionyl chloride and the halogenaylation was carried out at 60° C within 90 minutes.
Eksempel 16. Example 16.
Det sekundære butyl-halv-esterprodukt ble fremstilt under anvendelse av fremgangsmåten og molforholdene i eksempel 8 med unntagelse av at halv-esteren ble isomerisert ved 100 °C i 30 minutter under anvendelse av 0,28 vektprosent thionylklorid, og halogenaeyleringen ble ut-ført ved 45°C i løpet av 140 minutter. The secondary butyl half-ester product was prepared using the procedure and molar ratios of Example 8, except that the half-ester was isomerized at 100°C for 30 minutes using 0.28% by weight thionyl chloride, and the halogenaylation was carried out by 45°C within 140 minutes.
Eksempel 17. Example 17.
Allyl-halv-esterproduktet ble fremstilt under anvendelse av fremgangsmåten og molforholdene av reaksjonsmidlene i eksempel 8 med unntagelse av at halv-esteren ble isomerisert ved 90—100°C i 30 minutter under anvendelse av 0,50 vektprosent PCI., som isomeriseringskata-lysatoren, og halogenaeyleringen ble utført ved 65°C i løpet av 75 minutter. The allyl half-ester product was prepared using the procedure and molar ratios of the reactants in Example 8 except that the half-ester was isomerized at 90-100°C for 30 minutes using 0.50% by weight PCI as the isomerization catalyst. , and the halogenation was carried out at 65°C for 75 minutes.
Resultatene av de neste fem eksempler er vist i tabell V. The results of the next five examples are shown in Table V.
Eksempel 18. Example 18.
1 mol maleinsyreanhydrid (98 g) ble innveiet i en Morton-kolbe utstyrt som tidligere beskrevet. 1 mol methylamylalkohol (4-methyl-2-pentanol) (102 g) ble tilsatt gradvis i løpet av 35 minutter fra en drypetrakt mens reaksjonsblandingen ble holdt .ved 110°C. 0,68 g PCL 1 mole of maleic anhydride (98 g) was weighed into a Morton flask equipped as previously described. 1 mole of methylamyl alcohol (4-methyl-2-pentanol) (102 g) was added gradually over 35 minutes from a dropping funnel while maintaining the reaction mixture at 110°C. 0.68 g of PCL
(0,005 mol) ble tilsatt til reaksjonsblandingen (0.005 mol) was added to the reaction mixture
mens reagensene ble holdt ved 110°C i 10 minut-er. Umiddelbart deretter ble 200 g sojabønne-olje (1,9 ekvivalenter av ethylenisk umetthet) tilsatt til reaksjonsblandingen og reaksjonsblandingens temperatur ble regulert til 65°C. 112 g 97 psts. rent tertiært butylhypoklorit (1,0 mol) while the reagents were kept at 110°C for 10 minutes. Immediately thereafter, 200 g of soybean oil (1.9 equivalents of ethylenic unsaturation) was added to the reaction mixture and the temperature of the reaction mixture was adjusted to 65°C. 112 g 97 percent. pure tertiary butyl hypochlorite (1.0 mol)
ble deretter tilsatt reaksjonsblandingen i løpet av 20 minutter, mens reaksj onsbladingen ble holdt ved en temperatur av 65°C. Produktet ble isolert ved fremgangsmåten beskrevet i eksempel 8 (B) og derpå sampolymerisert med 30 vektprosent styren på samme måte. was then added to the reaction mixture over 20 minutes, while the reaction mixture was maintained at a temperature of 65°C. The product was isolated by the method described in example 8 (B) and then copolymerized with 30% by weight of styrene in the same way.
Eksempel 19. Example 19.
Eksempel 18 ble gjentatt med unntagelse av at 1,2 mol methylamylalkohol og 1,2 mol maleinsyreanhydrid ble anvendt. Example 18 was repeated with the exception that 1.2 mol of methylamyl alcohol and 1.2 mol of maleic anhydride were used.
Eksempel 20: Example 20:
Eksempel 8 ble gjentatt med unntagelse av at <1>4 av methylamylalkoholen ble erstattet med <1>4 mol isobutanol. Example 8 was repeated with the exception that <1>4 of the methylamyl alcohol was replaced by <1>4 mol of isobutanol.
Eksempel 21. Example 21.
2-ethylhexyl-halv-esterreaksjonsproduktet ble fremstilt under, anvendelse av fremgangsmåten og forholdene i henhold til eksempel 18. The 2-ethylhexyl half-ester reaction product was prepared using the method and conditions according to Example 18.
Eksempel 22. Example 22.
Tridecyl-halv-esterreaksjonsproduktet ble fremstilt under' anvendelse av fremgangsmåten og forholdene i henhold til eksempel 18. The tridecyl half-ester reaction product was prepared using the method and conditions of Example 18.
Eksempel 23. Example 23.
443 g castorolje (1,5 ekvivalenter av ethylenisk umettethet), 220,8 g methåcrylsyre (2,55 mol) som inneholdt 0,075 vektprosent p-methoxyfenol og 163,9 g 99 pst. rent tertiært butylhypoklorit (1,5 mol) ble brakt til reaksjon i 90 minutter ved 45 °C. Reaksjonsblandingen ble utdrevet ved 25 mm og 50°C for å fjerne det tertiære butylalkohol-biprodukt. Surhet og infra-rød spektrofotometrisk analyser av prøven viste at 42,5 molprosent av oljeumettethet ble omdannet til nabo-methacryloxy-klorderivat. Ytterligere analyse viste at 30 molprosent av oljeumettetheten var allylklorgrupper og at 22 molprosent av oljeumettetheten hadde butoxy-klorsubstituenter. 443 g of castor oil (1.5 equivalents of ethylenic unsaturation), 220.8 g of methacrylic acid (2.55 mol) containing 0.075% by weight of p-methoxyphenol and 163.9 g of 99% pure tertiary butyl hypochlorite (1.5 mol) were brought to reaction for 90 minutes at 45 °C. The reaction mixture was evaporated at 25 mm and 50°C to remove the tertiary butyl alcohol by-product. Acidity and infrared spectrophotometric analyzes of the sample showed that 42.5 mole percent of oil unsaturation was converted to neighboring methacryloxy-chloro derivative. Further analysis showed that 30 mole percent of the oil unsaturation was allyl chloro groups and that 22 mole percent of the oil unsaturation had butoxy-chloro substituents.
Det utdrevne produkt ble sampolymerisert med 33 vektprosent styren ,under anvendelse av 1 pst. benzoylperoxyd og 1 pst. barium-cadmium-carboxylat ved 65°C i 4 timer. The expelled product was copolymerized with 33% by weight of styrene, using 1% benzoyl peroxide and 1% barium cadmium carboxylate at 65°C for 4 hours.
Den støpte plate var gul, svakt opak, semi-hard og svakt fleksibel. The cast plate was yellow, slightly opaque, semi-hard and slightly flexible.
Eksempel 24. Example 24.
36,25 g menhadenolje (0,25 ekvivalenter av ethylenisk umettethet), 36,55 g methåcrylsyre (0,425 mol) inneholdende 0,025 vektprosent p-methoxyfenol og 27,1 g 99,6 pst. tertiært butylhypoklorit (0,25 mol) ble brakt til å reagere i 90-minutter ved 65°C. Reaksjonsblandingen ble utdrevet ved 25 mm trykk og 50°C. Surhet og in-frarød analyse viste at 46,7 molprosent av oljeumettetheten hadde methacryloxy- og klorsubstituenter. Ytterligere analyse viste at 14 molprosent av oljeumettetheten var allkylklorgrup-per og at 30 molprosent av oljeumettetheten hadde butoxy- og klorsubstituenter. Et sampolymer med 33 vektprosent styren var rødbrunt, transparent, hardt og sprøtt. 36.25 g of menhaden oil (0.25 equivalents of ethylenic unsaturation), 36.55 g of methacrylic acid (0.425 mol) containing 0.025 weight percent p-methoxyphenol and 27.1 g of 99.6 percent tertiary butyl hypochlorite (0.25 mol) were brought to react for 90 minutes at 65°C. The reaction mixture was expelled at 25 mm pressure and 50°C. Acidity and infrared analysis showed that 46.7 mole percent of the oil unsaturation had methacryloxy and chlorine substituents. Further analysis showed that 14 mole percent of the oil unsaturation was alkyl chloro groups and that 30 mole percent of the oil unsaturation had butoxy and chlorine substituents. A copolymer with 33% by weight styrene was reddish brown, transparent, hard and brittle.
Eksempel 25. Example 25.
33,2 g linfrøolje (0,25 ekvivalenter av ethylenisk umettethet) ble anvendt istedenfor 0,25 ekvivalenter av menhadenolje i eksempel 24. 57,5 molprosent ethyleniske grupper i oljen hadde methacryloxy- og klorsubstituenter, 14,4 molprosent av de ethyleniske grupper i oljen var klorallylgrupper og 12 molprosent av de ethyleniske grupper i oljen hadde butoxy -og klorsubstituenter. Et sampolymer med 33 vektprosent styren var rav-farget, transparent, hardt og stivt. 33.2 g of linseed oil (0.25 equivalents of ethylenic unsaturation) was used instead of 0.25 equivalents of menhaden oil in Example 24. 57.5 mole percent ethylenic groups in the oil had methacryloxy and chlorine substituents, 14.4 mole percent of the ethylenic groups in the oil was chlorallyl groups and 12 mole percent of the ethylenic groups in the oil had butoxy and chlorine substituents. A copolymer with 33% by weight styrene was amber colored, transparent, hard and rigid.
Eksempel 26. Example 26.
31,5 g tungolje (kinesisk treolje) (0,300 ekvivalenter av ethylenisk umettethet) ble blandet med 43,9 g (0,510 mol) methåcrylsyre inneholdende 0,025 pst. p-methoxyfenol. Denne blandingen ble brakt til reaksjon med 32,6 g (0,300 mol), tertiært butylhypoklorit i 90 minutter ved 65°C. Reaksjonsproduktet ble utdrevet ved 25 mm Hg og 50°C for å fjerne t-butylalkohol-biproduktet. Infrarøde spektrofotometriske analyser viste at 45,7 molprosent av oljeumettetheten var omdannet til nabo-methacryloxy-klorsubstituenter. Et sampolymer av oljeproduktet inneholdende 33 pst. (vektprosent) styren var klart, lysegult, ganske hardt og stivt. 31.5 g heavy oil (Chinese wood oil) (0.300 equivalents of ethylenic unsaturation) was mixed with 43.9 g (0.510 mol) methacrylic acid containing 0.025% p-methoxyphenol. This mixture was reacted with 32.6 g (0.300 mol) of tertiary butyl hypochlorite for 90 minutes at 65°C. The reaction product was expelled at 25 mm Hg and 50°C to remove the t-butyl alcohol by-product. Infrared spectrophotometric analyzes showed that 45.7 mole percent of the oil unsaturation had been converted to neighboring methacryloxy-chloro substituents. A copolymer of the oil product containing 33 wt.% styrene was clear, light yellow, fairly hard and rigid.
Eksempel 27. Example 27.
445 g methyloleat (1,5 ekvivalenter ethylenisk umettethet) ble anvendt istedenfor 1,5 ekvivalenter castorolje som i eksempel 23. Analyse av produktet viste at 60 molprosent ethylenisk umettede grupper i esteren hadde klor- og me-thacryloxysubstituenter. Et sampolymer med 33 vektprosent styren, som var blitt modnet ved 445 g of methyl oleate (1.5 equivalents of ethylenic unsaturation) was used instead of 1.5 equivalents of castor oil as in example 23. Analysis of the product showed that 60 mole percent ethylenically unsaturated groups in the ester had chlorine and methacryloxy substituents. A copolymer with 33% by weight styrene, which had been matured in wood
100 °C i 1 time etter den innledende sampolymerisering ved 65°C i 3 timer, var et seigt, ganske elastisk fast stoff som klebet seg til alumi-niumformen. 100°C for 1 hour after the initial copolymerization at 65°C for 3 hours, a tough, fairly elastic solid adhered to the aluminum mold.
Eksempel 28 til og med eksempel 36. Example 28 through Example 36.
En rekke talloljeestere ble brakt til å reagere med tertiært butylhypoklorit og methåcrylsyre inneholdende 0,05 pst. p-methoxyfenol ved 45°C under anvendelse av en konsentrasjon av 1,7 mol methåcrylsyre, 1,0 mol tertiært butylhypoklorit og tilstrekkelig talloljeester så at det inneholdt 1,0 ekvivalent ethylenisk umettethet. En del av prøvene ble utdrevet ved 50°C og 50 mm trykk og en annen del ble ekstrahert alka--lisk ved den fremgangsmåte som er beskrevet i eksempel 1. Tabell VI viser egenskapene av tall-oljeesterne som ble fremstilt ved vanlig forest-ringsteknikk. Tabell VII angir egenskapene av det halogenacylerte produkt, og tabell VIII angir egenskapene av et sampolymer av det vakuumbehandlete reaksjonsprodukt med 33 vektprosent styren. A series of tallow esters were reacted with tertiary butyl hypochlorite and methacrylic acid containing 0.05% p-methoxyphenol at 45°C using a concentration of 1.7 moles of methacrylic acid, 1.0 moles of tertiary butyl hypochlorite and sufficient tallow ester so that contained 1.0 equivalent of ethylenic unsaturation. Part of the samples were extracted at 50°C and 50 mm pressure and another part was extracted alkaline by the method described in example 1. Table VI shows the properties of the tall oil esters that were produced by the usual esterification technique . Table VII sets forth the properties of the halogenacylated product, and Table VIII sets forth the properties of a copolymer of the vacuum-treated reaction product with 33 weight percent styrene.
Som i de foregående eksempler er A det råreaksjonsprodukt, B er det vakuumbehandlete produkt og C er det alkalivaskete produkt. As in the previous examples, A is the raw reaction product, B is the vacuum-treated product and C is the alkali-washed product.
Eksempel 37. Example 37.
Et handelsvanlig tilgjengelig sojabønneolje-monoglyoerid med 3,87 mekv/g ethylenisk umettethet ble halogenacylert under anvendelse av de samme betingelser og forhold som ble anvendt i de foregående ni eksempler. Produktet hadde 33,7 molprosent acryloxy-klorgrupper, 23,5 molprosent butoxy-klorgrupper, 14,3 allylklorgrupper cg 0,45 acryloxygrupper pr. molekyl. Et sampolymer av det vakuumbehandlete produkt med 33 vektprosent styren var hardt, seigt og svakt elastisk. A commercially available soybean oil monoglyoeride with 3.87 meq/g of ethylenic unsaturation was haloacylated using the same conditions and conditions used in the previous nine examples. The product had 33.7 mole percent acryloxy chlorine groups, 23.5 mole percent butoxy chlorine groups, 14.3 allyl chlorine groups and 0.45 acryloxy groups per molecule. A copolymer of the vacuum-treated product with 33 weight percent styrene was hard, tough and slightly elastic.
Eksempel 38. Example 38.
Dette eksempel viser anvendelsen av tertiært amylhypoklorit. Sojabønneolje (40,0 g = 0,20 mol umettethet), methåcrylsyre (17,2 g = 0,20 mol) og p-methoxyfenol (0,05 vektprosent methåcrylsyre) ble blandet ved romtemperatur. Tertiært amylhypoklorit (27,2 g = 0,20 mol 90 pst.'s renhet) ble tilsatt langsomt i løpet av 18 minutter. Den eksotherme reaksjon ble holdt ved 40°C, først ved avkjøling, senere ved opphetning, inntil man fikk en negativ kalium jodidprøve f oi hypoklorit. This example shows the use of tertiary amyl hypochlorite. Soybean oil (40.0 g = 0.20 mol unsaturation), methacrylic acid (17.2 g = 0.20 mol) and p-methoxyphenol (0.05 wt% methacrylic acid) were mixed at room temperature. Tertiary amyl hypochlorite (27.2 g = 0.20 mol 90% purity) was added slowly over 18 minutes. The exothermic reaction was maintained at 40°C, first by cooling, later by heating, until a negative potassium iodide sample was obtained for hypochlorite.
Som beskrevet i de foregående eksempler ble en del av den totale reaksjonsblanding (prøve A) vakuumbehandlet for å fjerne t-amylalkohol-biproduktet og det ble tilbake et residuum (prøve B). En annen del av den totale reaksjonsblanding ble alkalivasket for å fjerne både t-amyl-alkohol og ureagert methåcrylsyre under dannelse av det isolerte oljeprodukt (prøve C). Den følgende tabell viser de analytiske dataer som ble oppnådd med de tre prøver. As described in the preceding examples, a portion of the total reaction mixture (sample A) was vacuum treated to remove the t-amyl alcohol by-product and a residue (sample B) remained. Another portion of the total reaction mixture was alkali washed to remove both t-amyl alcohol and unreacted methacrylic acid to form the isolated oil product (sample C). The following table shows the analytical data obtained with the three samples.
Beregninger basert på disse analyser, viste at sojabønneoljen ble omdannet til de følgende produkter. De kvantitative verdier er basert på mol umettethet i den opprinnelige sojabønne-olje. Calculations based on these analyses, showed that the soybean oil was converted into the following products. The quantitative values are based on moles of unsaturation in the original soybean oil.
En liten del av den flytende prøve B (9,90 g) ble blandet med styren (4,95 g) og benzoylperoxyd (0,15 g) og støpt i en form for å danne en plate med en tykkelse av 3,17 mm (1/8"). Støpningen ble opphetet ved 65 °C i 16 timer etterfulgt av en etterherdning av-30 minutter ved 120°C. Sampolymeret som ble dannet, var et gult, lysegult fast stoff. Det hadde en Clash-Berg elastisk modul T4-verdi av 38°C og en Barcol 935 hårdhets-verdi av 45—30. A small portion of the liquid sample B (9.90 g) was mixed with styrene (4.95 g) and benzoyl peroxide (0.15 g) and cast into a mold to form a plate with a thickness of 3.17 mm (1/8"). The casting was heated at 65°C for 16 hours followed by a post-cure of -30 minutes at 120°C. The copolymer formed was a yellow, pale yellow solid. It had a Clash-Berg elastic modulus T4 value of 38°C and a Barcol 935 hardness value of 45-30.
Eksempel 39. Example 39.
Dette eksempel viser anvendelsen av alumi-nium-klorid som en isomeriseringskatalysator. Maleinsyreanhydrid (98,0 g = 1,00 mol) ble opphetet til 110°C i et reaksjonskar utstyrt med en rører, en kondensator og et reaksjonsmiddeltil-føringsrør. Methylamylalkohol, dvs. 4-methyl-2-pentanol (102,0 g = 1,00 mol) ble tilsatt i løpet av 40 minutter, under regulering av den eksothermiske reaksjon ved 110—114°C. Denne reaksjonstemperatur ble opprettholdt i ytterligere 20 minutter, derpå ble reaksjonsblandingen avkjølt til 90°C. Aluminiumklorid (1,00 g = 0,0075 mol) This example shows the use of aluminum chloride as an isomerization catalyst. Maleic anhydride (98.0 g = 1.00 mol) was heated to 110°C in a reaction vessel equipped with a stirrer, a condenser and a reactant feed tube. Methylamyl alcohol, i.e. 4-methyl-2-pentanol (102.0 g = 1.00 mol) was added over 40 minutes, controlling the exothermic reaction at 110-114°C. This reaction temperature was maintained for a further 20 minutes, then the reaction mixture was cooled to 90°C. Aluminum chloride (1.00 g = 0.0075 mol)
ble tilsatt og temperaturen ble .regulert til 90°C was added and the temperature was regulated to 90°C
i løpet av 25 minutter. Sojabønneolje (200,0 g = 1,00 mol umettethet) og p-methoxyfenol (0,03 g = 0,015 mol) ble tilsatt hurtig og temperaturen within 25 minutes. Soybean oil (200.0 g = 1.00 mol unsaturation) and p-methoxyphenol (0.03 g = 0.015 mol) were added rapidly and the temperature
ble regulert til 65°C. Tertiært butylhypoklorit was regulated to 65°C. Tertiary butyl hypochlorite
(110,0 g = 1,00 mol 98,5 pst.'s renhet) ble tilsatt (110.0 g = 1.00 mol 98.5% purity) was added
i løpet av 60 minutter under regulering av den eksothermiske reaksjon ved 65—70°C. Denne reaksjonstemperatur ble opprettholdt i ytterligere 30 minutter. Trykket ble redusert til 25 mm Hg under opprettholdelse av en temperatur av 65—70 °C og ved kraftig blanding ble det tertiære butylalkohol-biprodukt fjernet ved destillering. during 60 minutes under control of the exothermic reaction at 65-70°C. This reaction temperature was maintained for a further 30 minutes. The pressure was reduced to 25 mm Hg while maintaining a temperature of 65-70°C and by vigorous mixing the tertiary butyl alcohol by-product was removed by distillation.
Produktet var en klar, lysegul væske med en viskositet av 5000 eps ved 25°C. Sampolymerisering med styren gav et bøyelig harpiks med en strekkstyrke av 35 kg/cma (500 psi) og en elastisitetsmodul T, av 20°C. The product was a clear, pale yellow liquid with a viscosity of 5000 eps at 25°C. Copolymerization with styrene produced a flexible resin with a tensile strength of 35 kg/cma (500 psi) and a modulus of elasticity T, of 20°C.
Eksempel 40. Example 40.
Methåcrylsyre (117 g = 1,35 mol) inneholdende 0,025 pst. p-methoxyfenol og sojabønne-olje (200 g --- 1,00 mol umettethet) ble blandet og opphetet til 65°C. Tertiært butylhypoklorit (110 g = 1,00 mol) 9,85 pst.'s renhet ble tilsatt langsomt i løpet av 30 minutter under kontroll av den eksotherme reaksjon ved 65—70°C. Denne reaksjonstemperatur ble opprettholdt i ytterligere 90 minutter. Trykket ble redusert til 25 mm Hg, og ved å holde temperaturen ved 65— 70°C og blande kraftig ble det tertiære butyl-alkoholbiprodukt fjernet ved destillering. Methacrylic acid (117 g = 1.35 mol) containing 0.025% p-methoxyphenol and soybean oil (200 g --- 1.00 mol unsaturation) were mixed and heated to 65°C. Tertiary butyl hypochlorite (110 g = 1.00 mol) 9.85% purity was added slowly over 30 minutes under control of the exothermic reaction at 65-70°C. This reaction temperature was maintained for a further 90 minutes. The pressure was reduced to 25 mm Hg, and by maintaining the temperature at 65-70°C and mixing vigorously, the tertiary butyl alcohol by-product was removed by distillation.
De kjemiske og fysikalske egenskaper av det klare, lysegule flytende produkt var som følger: The chemical and physical properties of the clear, pale yellow liquid product were as follows:
D D
Brookfield viskositet, eps ved 25°C 730 Brookfield viscosity, eps at 25°C 730
Sojaoljeproduktet (66 deler) ble forent med styren (33 deler) og benzoylperoxyd (1 del), støpt til en plate med 3 mm (1/8 inch) tykkelse, og herdet i 16 timer ved 65°C og 1/2 time ved 110°C. Sampolymeret hadde følgende fysikalske egenskaper: The soybean oil product (66 parts) was combined with styrene (33 parts) and benzoyl peroxide (1 part), molded into a plate 3 mm (1/8 inch) thick, and cured for 16 hours at 65°C and 1/2 hour at 110°C. The copolymer had the following physical properties:
Skjærmodul, (302,000 pst) (flexural Shear modulus, (302,000 pst) (flexural
modulus) 21.233 kg/cms modulus) 21.233 kg/cms
Dette eksempel ble gjentatt under anvendelse av et annet forhold for reaksjonsmidlene; methåcrylsyre (56,5 g = 0,65 mol) inneholdende 0,025 pst. p-methoxyfenol, sojabønneolje (200 g = 1,00 mol umettethet )og t-butylhypoklorit (110 g = .1,00 mol 98,5 pst.'s renhet). This example was repeated using a different ratio of the reactants; methacrylic acid (56.5 g = 0.65 mol) containing 0.025 percent p-methoxyphenol, soybean oil (200 g = 1.00 mol unsaturation) and t-butyl hypochlorite (110 g = 1.00 mol 98.5 percent). s purity).
Sojaoljeproduktet som ble sampolymerisert med 33 pst. styren hadde følgende fysikalske egenskaper: The soybean oil product that was copolymerized with 33 percent styrene had the following physical properties:
Eksempel 41. Example 41.
En blanding av hepten-3 (høy renhet) (49,0 g = 0,50 mol), methåcrylsyre (43,3 g = 0,50 mol) og p-methoxyfenol (0,022 g = 0,05 pst. methåcrylsyre) ble" opphetet til 60°C. Tertiært butylhypoklorit (54,5 g = 0,50 mol) ble langsomt tilsatt under opprettholdelse av den eksotherme reaksjon ved 65 °C ved ytre kjøling. Etter 140 minutter ved 65 °C gav blandingen en negativ kaliumjodidprøve like overfor hypoklorit. En prøve av de totale reaksjonsprodukter ble merket Halvparten av produktet ble opphetet ved 55°C og trykket ble redusert til 12 mm Hg. Herved ble mesteparten av t-butylalkohol-biproduktet fjernet ved destillering. Det flytende medium ble kalt prøve «B». A mixture of heptene-3 (high purity) (49.0 g = 0.50 mol), methacrylic acid (43.3 g = 0.50 mol) and p-methoxyphenol (0.022 g = 0.05% methacrylic acid) was " heated to 60°C. Tertiary butyl hypochlorite (54.5 g = 0.50 mol) was slowly added while maintaining the exothermic reaction at 65°C with external cooling. After 140 minutes at 65°C the mixture gave a negative potassium iodide sample equal to against hypochlorite. A sample of the total reaction products was labeled Half of the product was heated at 55°C and the pressure was reduced to 12 mm Hg. This removed most of the t-butyl alcohol by-product by distillation. The liquid medium was called sample "B ».
Den andre halvpart av de totale reaksjonsprodukter ble oppløst i to volumdeler ethyleter. Denne etheroppløsning ble først vasket med 3 pst. vandig Na2HP04-oppløsning inntil den ble alkalisk og derpå med fortynnet vann inntil den The other half of the total reaction products was dissolved in two volumes of ethyl ether. This ether solution was first washed with 3% aqueous Na 2 HPO 4 solution until it became alkaline and then with dilute water until
ble svakt sur (pH 5,5—6,0). Paramethoxyfenol (0,02 vektprosent av produktet )ble tilsatt og det became slightly acidic (pH 5.5-6.0). Paramethoxyphenol (0.02% by weight of the product) was added and that
etheriske oppløsningsmiddel ble fjernet ved vakuumdestillering ved 65°C og 25 mm Hg. Det flytende residuum ble merket prøve «C». ethereal solvents were removed by vacuum distillation at 65°C and 25 mm Hg. The liquid residue was labeled sample "C".
Den følgende tabell viser de analytiske data The following table shows the analytical data
som ble erholdt med A- og C-prøvene. which was obtained with the A and C samples.
Beregninger basert på disse analyser viste at hepten-3 ble omdannet til følgende produkter: Calculations based on these analyzes showed that heptene-3 was converted into the following products:
En liten del av «B»-prøven ble blandet med 2 pst. benzoin, støpt i en cellofanform og utsatt A small portion of the "B" sample was mixed with 2% benzoin, cast into a cellophane mold and exposed
for ultrafiolett lys i 2 timer. Den polymeriserte til et vannklart, hardt, stivt fast stoff. En annen del av prøven «B» ble sampolymerisert på lignende måte med 30 pst. styren så at man fikk et lysegult, hardt, opakt, sprøtt fast stoff. En liten del av «C»-prøven ble homopolymerisert på lignende måte så at man fikk et lysegult, opakt, sprøtt fast stoff som var hardere enn B-homopolymeret. for ultraviolet light for 2 hours. It polymerized into a water-clear, hard, rigid solid. Another portion of sample "B" was copolymerized in a similar manner with 30% styrene to give a pale yellow, hard, opaque, brittle solid. A small portion of the "C" sample was homopolymerized in a similar manner to give a pale yellow, opaque, brittle solid that was harder than the B homopolymer.
Eksempel 42. Example 42.
Dette eksempel viser halogenaeyleringen. av methåcrylsyre med et annet methacrylsyremole-kyl. Tertiært butylhypoklorit (27 g = 0,25 mol) ble langsomt tilsatt til methåcrylsyre (43 g = 0,50 mol) inneholdende 0,05 pst. p-methoxyfenol. Man kunne ikke se at det fant sted eksotherm reaksjon selv når blandingen ble opphetet til 45 °C og holdt ved denne temperatur i 20 minutter. Blandingen ble kastet bort. This example shows the halogenayl ring. of methacrylic acid with another methacrylic acid molecule. Tertiary butyl hypochlorite (27 g = 0.25 mol) was slowly added to methacrylic acid (43 g = 0.50 mol) containing 0.05% p-methoxyphenol. No exothermic reaction could be seen even when the mixture was heated to 45°C and held at this temperature for 20 minutes. The mixture was discarded.
Tertiært butylhypoklorit (109,0 g = 1,0 mol) ble tilsatt langsomt til methåcrylsyre (86,5 g .= 1,0 mol) inneholdende p-methoxyfenol (0,025 pst) og tetramethylammoniumklorid (0,33 g = 0,003 mol). Det fant øyeblikkelig sted kraftig eksotherm reaksjon. Temperaturen ble holdt ved 65 °C inntil negativ kaliumj odidprøve like overfor hypoklorit. Som i eksempel 41 ble «B»-prøven fremstilt ved å fjerne t-butylalkoholbiproduktet ved vakuumdestillering. Tertiary butyl hypochlorite (109.0 g = 1.0 mol) was added slowly to methacrylic acid (86.5 g .= 1.0 mol) containing p-methoxyphenol (0.025 pst) and tetramethylammonium chloride (0.33 g = 0.003 mol). A vigorous exothermic reaction immediately took place. The temperature was maintained at 65 °C until negative potassium iodide test just opposite hypochlorite. As in Example 41, the "B" sample was prepared by removing the t-butyl alcohol by-product by vacuum distillation.
Fra analyser lignende de i eksempel 41 viste beregninger at 66 molprosent methåcrylsyre reagerte med seg selv så at det ble dannet klor-methacryloxykondensat. Produktet inneholdt 16 molprosent klorbutoxyderivat og 16 molprosent vinylumettethet. From analyzes similar to those in example 41, calculations showed that 66 mole percent methacrylic acid reacted with itself so that chlorine-methacryloxy condensate was formed. The product contained 16 mole percent chlorobutoxy derivative and 16 mole percent vinyl unsaturation.
Det flytende «B»-produkt ble homopolymerisert under anvendelse av benzoylperoxyd og 65°C opphetning. Det frembrakte et bløtt, klart, ganske seigt fast stoff. The liquid "B" product was homopolymerized using benzoyl peroxide and 65°C heating. It produced a soft, clear, fairly tough solid.
Eksempel 43. Example 43.
Dette eksempel viser den foretrukkede halo-genacrylering av methacryl og med et andre molekyl av methåcrylsyre i nærvær av tetraklorethylen. This example shows the preferred halogenacrylation of methacrylic with a second molecule of methacrylic acid in the presence of tetrachloroethylene.
En blanding av tetraklorethylen (83 g = 0,5 mol) og methåcrylsyre (65—0,75 mol) ble fremstilt inneholdende 0,327 g (0,003 mol) tetramethylammoniumklorid. Tertiært butylhypoklorit (55 g — 0,50 mol) ble tilsatt dråpevis til blandingen ved 25°C. Ved tilsetning av 1—2 g t-butylhypoklorit steg temperaturen med én gang til 35°C. Denne temperatur ble opprettholdt ved isbadkjøling under tilsetning av det resterende hypoklorit. 80 minutter etter tilset-ningen av t-butylhypokloritet var KI-prøven negativ likeoverfor det. A mixture of tetrachlorethylene (83 g = 0.5 mol) and methacrylic acid (65-0.75 mol) was prepared containing 0.327 g (0.003 mol) of tetramethylammonium chloride. Tertiary butyl hypochlorite (55 g - 0.50 mol) was added dropwise to the mixture at 25°C. On addition of 1-2 g of t-butyl hypochlorite, the temperature rose immediately to 35°C. This temperature was maintained by ice bath cooling while adding the remaining hypochlorite. 80 minutes after the addition of t-butyl hypochlorite, the KI sample was negative opposite it.
Materialets flyktighet ved en reaksjonstemperatur av 62°C og 12 mm Hg ble fjernet fra en del av den totale reaksjonsblanding ved destillering. Kjemisk analyse av den totale reaksjonsblanding og av residuet fra destilleringen viste at tetraklorethylenet ikke reagerte. Hovedreak-sjonsproduktet var klormethacryloxykonden-satet som stammet fra methacrylsyren. Omtrent 0,40 mol av methacrylsyreumettetheten ble omdannet til klormethacryloxyderivatet og 0,07 mol til klorbutoxyderivatet. The volatility of the material at a reaction temperature of 62°C and 12 mm Hg was removed from a portion of the total reaction mixture by distillation. Chemical analysis of the total reaction mixture and of the residue from the distillation showed that the tetrachlorethylene did not react. The main reaction product was the chloromethacryloxy condensate derived from the methacrylic acid. About 0.40 mol of the methacrylic acid unsaturation was converted to the chloromethacryloxy derivative and 0.07 mol to the chlorobutoxy derivative.
En blanding av 4,0 g av det flytende destil-lasjonsresiduum og 0,05 g benzoylperoxyd ble støpt i en form så at man fikk en plate av ca. 1,5 mm tykkelse (1/16"). Etter opphetning i 16 timer ved 65°C og 0,5 time ved 120°C fikk man et klart, hardt, sprøtt harpiks. A mixture of 4.0 g of the liquid distillation residue and 0.05 g of benzoyl peroxide was cast into a mold so that a plate of approx. 1.5 mm thickness (1/16"). After heating for 16 hours at 65°C and 0.5 hour at 120°C, a clear, hard, brittle resin was obtained.
Eksempel 44. ' Example 44. '
Tertiært butylhypoklorit (76,3 g — 0,70 mol) ble tilsatt langsomt til. en blanding av allylklorid (53,5 g — 0,80 mol), methåcrylsyre (90,8 g — 1,05 mol) og tetramethylammoniumklorid (0,23 g — 0,0021 mol). Den eksotherme reaksjon ble opprettholdt ved 45°C ved ytre kjøling. Innen 40 minutter var en KI-prøve negativ like overfor hypoklorit. Tertiary butyl hypochlorite (76.3 g - 0.70 mol) was added slowly to. a mixture of allyl chloride (53.5 g — 0.80 mol), methacrylic acid (90.8 g — 1.05 mol) and tetramethylammonium chloride (0.23 g — 0.0021 mol). The exothermic reaction was maintained at 45°C by external cooling. Within 40 minutes, a KI sample was negative for hypochlorite.
Materialets flyktighet ved 18 mm Hg og en reaksjonstemperatur av 65°C ble fjernet fra en del av den totale reaksjonsblanding ved destillering. Man fikk et 69 pst.'s utbytte av residuum-produkt. Kjemisk analyse av den totale reaksjonsblanding og av residuet viste at 0,34 mol klormethacryloxymethacrylsyrekondensat var de to hovedprodukter som ble dannet. The volatility of the material at 18 mm Hg and a reaction temperature of 65°C was removed from a portion of the total reaction mixture by distillation. A 69 percent yield of residuum product was obtained. Chemical analysis of the total reaction mixture and of the residue showed that 0.34 mol of chloromethacryloxymethacrylic acid condensate were the two main products formed.
En blanding av 4,0 g av det flytende residuum, 2,0 g styren og 0,50 g benzoxylperoxyd ble opphetet i en lukket form ved 65 °C i 4 timer. Det ble dannet et vann-klart, hardt, sprøtt fast stoff. A mixture of 4.0 g of the liquid residue, 2.0 g of styrene and 0.50 g of benzoxyl peroxide was heated in a closed mold at 65°C for 4 hours. A water-clear, hard, brittle solid was formed.
Eksempel 45. Example 45.
Tertiært butylhypoklorit (54,5 g — 0,50 mol) ble forenet med en blanding av octadecen-1 (126,0 g — 0,50 mol), acrylsyre (36,3 g — 0,50 mol) og p-methoxyfenol (0,05 vektprosent acrylsyre). Reaksjonsfremgangsmåten og produktisoleringen ble utført på samme måte som i eksempel 41. Denne reaksjon var imidlertid lang-sommere og tok 210 minutter ved 65°C. Tertiary butyl hypochlorite (54.5 g — 0.50 mol) was combined with a mixture of octadecene-1 (126.0 g — 0.50 mol), acrylic acid (36.3 g — 0.50 mol) and p-methoxyphenol (0.05 weight percent acrylic acid). The reaction procedure and product isolation were carried out in the same way as in Example 41. However, this reaction was longer and took 210 minutes at 65°C.
Beregninger basert på analyse av A- og C-prøvene viste dannelsen av 68 molprosent klor-acryloxyoctadecan, 10 molprosent klorbutoxy-octadecan og 22 molprosent klorert octadecan-1. Calculations based on analysis of the A and C samples showed the formation of 68 mole percent chloroacryloxyoctadecane, 10 mole percent chlorobutoxyoctadecane and 22 mole percent chlorinated octadecane-1.
Polymerisering av den flytende B-prøven under anvendelse av 1 pst. benzoylperoxyd og 65°C i 16 timer plus 120°C i y2 time gav et bløtt, klebrig, gummiaktig stoff. Polymerization of the liquid B sample using 1% benzoyl peroxide and 65°C for 16 hours plus 120°C for y2 hours gave a soft, sticky, gummy substance.
Eksempel 46. Example 46.
Tertiært butylhypoklorit (54,5 g 0,50 mol) ble forenet med en blanding av cycloocten (55 g Tertiary butyl hypochlorite (54.5 g 0.50 mol) was combined with a mixture of cyclooctene (55 g
— 0,50 mol), acrylsyre (36,3 g — 0,50 mol) og p-methoxyfenol (0,05 pst. av acrylsyren). Reaksjonsfremgangsmåten og produktisoleringen ble — 0.50 mol), acrylic acid (36.3 g — 0.50 mol) and p-methoxyphenol (0.05 percent of the acrylic acid). The reaction procedure and product isolation were
utført på samme måte som i eksempel 41. Denne reaksjon var fullstendig i løpet av 50 minutter. carried out in the same manner as in Example 41. This reaction was complete within 50 minutes.
Beregninger baser på analyse av A- og C-prøvene viste dannelsen av 70 molprosent klor-acryloxy cyclooctan. Calculations based on analysis of the A and C samples showed the formation of 70 mole percent chloro-acryloxy cyclooctane.
Polymerisering av den flytende B-prøven under anvendelse av 1 pst. benzoylperoxyd og 65° C gav et klart, bløtt, ganske sterkt fast stoff som var sprøtt når det ble bøyet raskt. Polymerization of the liquid B sample using 1% benzoyl peroxide and 65°C gave a clear, soft, fairly strong solid which was brittle when bent rapidly.
Eksempel 47. Example 47.
Tertiært butylhypoklorit (54,5 g — 0,50 mol) ble forenet med en blanding av styren (52,0 g — 0,50 mol) og p-methoxyfenol (0,05 vektprosent acrylsyre). Reaksjonsforløpet og produktisoleringen som beskrevet i eksempel 41 ble fulgt. Denne reaksjon var fullstendig i løpet av 60 minutter. Tertiary butyl hypochlorite (54.5 g - 0.50 mol) was combined with a mixture of styrene (52.0 g - 0.50 mol) and p-methoxyphenol (0.05 wt% acrylic acid). The course of the reaction and product isolation as described in Example 41 was followed. This reaction was complete within 60 minutes.
Beregninger basert på analyse av A- og C-prøvene viste dannelsen av 42 molprosent nabo-kloracryloxyethylbenzen og 34 molprosent nabo-klorbutoxyethylbenzen. Calculations based on analysis of the A and C samples showed the formation of 42 mole percent neighboring chloroacryloxyethylbenzene and 34 mole percent neighboring chlorobutoxyethylbenzene.
Polymerisering av den flytende B-prøven under anvendelse av 1 pst. benzoylperoxyd og 65°C gav et meget bløtt, klebrig, halv-fast stoff. Polymerization of the liquid B sample using 1% benzoyl peroxide and 65°C gave a very soft, sticky, semi-solid.
Eksempel 48. Example 48.
Tertiært butylhypoklorit (54,5 g — 0,50 mol) ble forenet med en blanding av dicyclopentadien (66,0 g — 0,50 mol), methåcrylsyre (43,3 g — 0,50 mol) og p-methoxyfenol (0,05 vektprosent av methacrylsyren). Reaksjonsforløpet og produktisoleringen beskrevet i eksempel 41 ble fulgt. Denne reaksjon var fullstendig i løpet av 30 minutter. Tertiary butyl hypochlorite (54.5 g - 0.50 mol) was combined with a mixture of dicyclopentadiene (66.0 g - 0.50 mol), methacrylic acid (43.3 g - 0.50 mol) and p-methoxyphenol (0 .05 weight percent of the methacrylic acid). The course of the reaction and product isolation described in Example 41 was followed. This reaction was complete within 30 minutes.
Beregninger basert på analysen av A- og C-prøvene viste dannelsen av 54 molprosent klor-methacryloxyderivat og 14 pst. klorbutoxyderivat av dicyclopentadienet. Calculations based on the analysis of the A and C samples showed the formation of 54 mole percent chloromethacryloxy derivative and 14 percent chlorobutoxy derivative of the dicyclopentadiene.
Polymerisering av den flytende B-prøven under anvendelse av 1 pst. benzoylperoxyd og 65°C gav et sort, bløtt, gellignende stoff. Polymerization of the liquid B sample using 1% benzoyl peroxide and 65°C gave a black, soft, gel-like substance.
Eksempel 49. Example 49.
En blanding av methåcrylsyre (86,5 g — 1,00 mol), p-methoxyfenol (0,0432 g — 0,05 pst. av methacrylsyren) og tertiært butylhypoklorit (109,0 g — 1,00 mol) ble opphetet til 37°C i en reaksjonskolbe forsynt med en rører, et gassdis-pergeringsinnløpsrør, , termometer og en tørr ismethanolavkjølt kondensator. Ethylen (11,0 g — 0,393 mol) ble tilsatt til reaksjonsblandingen med en hastighet av 0,073 g/min. Den eksotherme reaksjon ble kontrollert ved 40—44°C ved isvannbadkj øling. A mixture of methacrylic acid (86.5 g — 1.00 mol), p-methoxyphenol (0.0432 g — 0.05 percent of the methacrylic acid) and tertiary butyl hypochlorite (109.0 g — 1.00 mol) was heated to 37°C in a reaction flask equipped with a stirrer, a gas dispersion inlet tube, , thermometer and a dry ice methanol-cooled condenser. Ethylene (11.0 g - 0.393 mol) was added to the reaction mixture at a rate of 0.073 g/min. The exothermic reaction was controlled at 40-44°C by ice water bath cooling.
Produktisolering var den samme som beskrevet i eksempel 41. C-produktet som ble isolert etter alkalisk vandig vasking, ble analysert som følger: Product isolation was the same as described in Example 41. The C product isolated after alkaline aqueous washing was analyzed as follows:
Etter forening med 1 pst. benzoylperoxyd og opphetning ved 65°C i 16 timer polymeriserte denne flytende C-produkt til et klart, blekgult, bløtt, tøyelig fast stoff. After combining with 1% benzoyl peroxide and heating at 65°C for 16 hours, this liquid product C polymerized to a clear, pale yellow, soft, ductile solid.
Eksempel 50. Example 50.
En blanding av methåcrylsyre (86,5 g — 1,90 mol), p-cresol (0,065 g — 0,075 pst. av methacrylsyren) og t-butylhypoklorit (109,0 g — 1,00 mol) ble opphetet til 39°C. Propylen (17,3 g — 0,412 mol) ble tilsatt med en hastighet av 0,25 g/minutt ved regulering av den eksotherme reaksjon ved 45°C. A mixture of methacrylic acid (86.5 g — 1.90 mol), p-cresol (0.065 g — 0.075 percent of the methacrylic acid) and t-butyl hypochlorite (109.0 g — 1.00 mol) was heated to 39°C . Propylene (17.3 g - 0.412 mol) was added at a rate of 0.25 g/minute by controlling the exothermic reaction at 45°C.
Produktisolering var den samme som beskrevet i eksempel 41. C-produktet som ble isolert etter alkaliske vandige vaskinger ble analysert som følger: Product isolation was the same as described in Example 41. The C product isolated after alkaline aqueous washes was analyzed as follows:
Etter forening med 1 pst. benzoylperoxyd og opphetning ved 65°C i 16 timer, polymeriserte dette flytende C-produkt til et klart, blekgult, bløtt, bøyelig, fast stoff. After combining with 1% benzoyl peroxide and heating at 65°C for 16 hours, this liquid product C polymerized to a clear, pale yellow, soft, pliable, solid.
Eksempel 51— 60. Example 51— 60.
Den følgende tabell IX beskriver i grove trekk utseendet av sampolymerstøpene som ble dannet fra et nabomethacryloxyklor-sojabønne-oljederivat. I hvert tilfelle ble 75 vektdeler av sojabønneoljederivatet fremstilt i henhold til eksempel 40 forenet med 25 vektdeler av det spesifiserte sam-monomer og 2 vektdeler ben-zoylperoxydpasta (en 50/50 blanding av benzoylperoxyd og tricresylfosfat). Eksempel nr. 53, 56, 57 og 58 ble polymerisert med 0,5 deler N,N-dimethylanilin ved romtemperatur i ca. 4 timer, derpå etterbehandlet ved 60°C i 3 timer. Alle de andre eksemplene ble polymerisert ved opphetning ved 70° C i 16 timer etterfulgt av en etterbehandling ved 120°C i % time. The following Table IX outlines the appearance of the copolymer casts which were formed from a neighboring methacryloxychloro-soybean oil derivative. In each case, 75 parts by weight of the soybean oil derivative prepared according to Example 40 was combined with 25 parts by weight of the specified co-monomer and 2 parts by weight of benzoyl peroxide paste (a 50/50 mixture of benzoyl peroxide and tricresyl phosphate). Example No. 53, 56, 57 and 58 were polymerized with 0.5 parts of N,N-dimethylaniline at room temperature for approx. 4 hours, then post-treated at 60°C for 3 hours. All the other samples were polymerized by heating at 70°C for 16 hours followed by a post-treatment at 120°C for 1 hour.
Som angitt ovenfor vedrører denne oppfinnelse fremstillingen av nabo-acryloxy-halogen-langkjedete alifatiske forbindelser. Skjønt den ovenfor angitte beskrivelse vedrører fremstillingen av disse forbindelser ved at en langkjedet ethylenisk umettet forbindelse og en sur acrylforbindelse og et alkylhypohalogenit bringes til å reagere med hverandre, så kan disse forbindelser og polymeriserbare komposisjoner basert på disse også fremstilles ved en av de følgende fremgangsmåter. 1. Reaksjon av en passende ethylenisk umettet langkjedet komposisjon med en passende acrylsyre, og fritt halogen i nærvær av en alkalisk katalysator. Et eksempel på denne fremgangsmåte er reaksjonen av en blanding av methyloleat, calciumacrylat, acrylsyre og tetramethyl-ammoni-umklorid med klor, så at man får en blanding av methylesterne av 9-acryloxy-19-klorstearinsyre og 9-klor-10-acryloxystearinsyre. 2. Reaksjon av en passende nabo-epoxy-langkjedet komposisjon med et passende acylr halogenid. Et eksempel på denne fremgangsmåte er reaksjonen av 9,10-epoxymethyloleat med acrylylklorid for å gi en blanding av methyl-9-acryloxy-10-klorstearat og methyl-9-klor-10-ac-ryloxystearat. As indicated above, this invention relates to the preparation of neighboring acryloxy-halogen long-chain aliphatic compounds. Although the above description relates to the production of these compounds by reacting a long-chain ethylenic unsaturated compound and an acidic acrylic compound and an alkyl hypohalogenite with each other, these compounds and polymerizable compositions based on them can also be produced by one of the following methods. 1. Reaction of a suitable ethylenically unsaturated long chain composition with a suitable acrylic acid, and free halogen in the presence of an alkaline catalyst. An example of this method is the reaction of a mixture of methyl oleate, calcium acrylate, acrylic acid and tetramethylammonium chloride with chlorine, so that a mixture of the methyl esters of 9-acryloxy-19-chlorostearic acid and 9-chloro-10-acryloxystearic acid is obtained. 2. Reaction of a suitable neighboring epoxy long chain composition with a suitable acyl halide. An example of this process is the reaction of 9,10-epoxymethyloleate with acrylic chloride to give a mixture of methyl-9-acryloxy-10-chlorostearate and methyl-9-chloro-10-acryloxystearate.
Alkylhypohalogenltfremgangsmåten er å foretrekke. Denne fremgangsmåte har to fordeler like overfor acylhalogenidmetoden: for det første er de umettede langkjedete materialer mindre kostbare enn de tilsvarende epoxykomposisjoner, da sistnevnte fåes i alminnelighet fra de først-nevnte, og for det annet er de frie acrylsyrer mindre kostbare enn de tilsvarende syrehalo-genider. Den har en hovedfordel like overfor den frie halogenmetode: utbyttene av de ønskede acryloxyhalogenkomposisjoner er høyere. The alkyl hypohalogen method is preferred. This method has two advantages over the acyl halide method: firstly, the unsaturated long-chain materials are less expensive than the corresponding epoxy compositions, as the latter are generally obtained from the first-mentioned, and secondly, the free acrylic acids are less expensive than the corresponding acid halo- genides. It has a main advantage over the free halogen method: the yields of the desired acryloxyhalogen compositions are higher.
Eksempel 61. Example 61.
Dette eksempel viser et nabo-acryloxy-klor-sojabønneoljederivat fremstilt ved å la epoxydisert sojabønneolje reagere med acrylklorid. 12y2 g epoxydisert sojabønneolje som inneholder 6,4 pst. ethylenoxydoxygen ble tilsatt dråpevis under omrøring ved 25°C til 4,53 g acrylylklorid. Blandingen som til å begynne med inneholdt 0,05 mol ethylenoxydoxygen og 0,05 mol syre-klorid, ble beskyttet mot atmosfæriske fuktighet. This example shows a neighboring acryloxy-chloro-soybean oil derivative prepared by reacting epoxidized soybean oil with acrylic chloride. 12y2g of epoxidized soybean oil containing 6.4% ethyleneoxydoxygen was added dropwise with stirring at 25°C to 4.53g of acrylic chloride. The mixture, which initially contained 0.05 moles of ethyleneoxydoxygen and 0.05 moles of acid chloride, was protected from atmospheric moisture.
30 minutter senere var reaksjonsblandingens ethylenoxydoxygeninnhold falt fra den opprinnelige verdi av 4,7 til 4,6 pst. Blandingen ble derpå opphetet i 1 time ved 80°C. Herved falt 30 minutes later, the ethyleneoxydoxygen content of the reaction mixture had fallen from the original value of 4.7 to 4.6%. The mixture was then heated for 1 hour at 80°C. Hereby fell
ethylenoxydoxygeninnholdet til 3,24 pst. En ny times opphetning ved 80°C senket ethylenoxydoxygeninnholdet i blandingen til 2,16 pst. Reaksj onsblandingen ble derpå opphetet i y2 time ved 100°C, avkjølt til 25°C og analysert med hensyn til totalsyretall, ethylenoxydoxygen og forsåpningstall. Disse verdier var henholdsvis 0,91, 0,91 og 6,85 mekv/g. Basert på disse analytiske verdier hadde ca. 62 pst. av acrylylkloridet reagert med den epoxydiserte sojabønneolje, 81 pst. av epoxygruppene var blitt spaltet opp, og åpenbart var 23 pst. av acrylylkloridet gått tapt ved for-dampning under reaksjonen. 10 g av den avkjølte reaksjonsblanding ble blandet med 0,1 g benzoylperoxyd oppløst i 0,3 g styren og opphetet i 1 time ved en temperatur varierende fra 70 til 80°C. Reaksjonsblandingen polymeriserte til et bløtt, bøyelig, vannklart, fast materiale. the ethyleneoxydoxygen content to 3.24%. A further hour of heating at 80°C lowered the ethyleneoxydoxygen content in the mixture to 2.16%. The reaction mixture was then heated for y2 hours at 100°C, cooled to 25°C and analyzed with regard to total acid number, ethyleneoxydoxygen and saponification number. These values were respectively 0.91, 0.91 and 6.85 meq/g. Based on these analytical values, approx. 62 percent of the acrylic chloride reacted with the epoxidized soybean oil, 81 percent of the epoxy groups had been cleaved, and apparently 23 percent of the acrylic chloride had been lost by evaporation during the reaction. 10 g of the cooled reaction mixture was mixed with 0.1 g of benzoyl peroxide dissolved in 0.3 g of styrene and heated for 1 hour at a temperature varying from 70 to 80°C. The reaction mixture polymerized to a soft, pliable, water-clear, solid material.
Eksempel 62. Example 62.
Dette eksempel viser et nabo-methacryloxy-bromderivat av sojabønneolje, og styren-sampolymer derav, fremstilt ved å la epoxydisert sojabønneolje reagere med methacrylylbromid. This example shows a neighboring methacryloxy bromo derivative of soybean oil, and styrene copolymer thereof, prepared by reacting epoxidized soybean oil with methacrylyl bromide.
A. Fremstilling av methacrylylbromid — I en 300 ml rundglasskolbe forsynt med kondensator, termometer, dryppetrakt og mekanisk rører ble anbrakt 59,6 g (0,22 mol) fosfortribromid. Kolben ble nedsenket i et isvahnbad. Methåcrylsyre (43 g, 0,5 mol) ble gradvis tilsatt til den omrørte fosfortribromid gjennom dryppetrakten i løpet av en tidsperiode av 2 timer. Reaksjonsblandingen omrøres i ytterligere 5 timer, i løpet av hvilken tid reaksjonsblandingens temperatur steg til ca. 40 °C. Blandingen lot man derpå henstå i 16 timer i en kjøler ved 8°C. Fos-forsyrlinglaget skilles fra methacrylylbromidla-get i en skilletrakt, og sistnevnte destilleres derpå under redusert trykk. Utbytte av hovedfrak-sjonen som koker ved 43,5—45,0°C ved 40 mm Hg trykk var 32 g eller 43 pst. av teorien. A. Preparation of methacrylyl bromide — Into a 300 ml round glass flask fitted with a condenser, thermometer, dropping funnel and mechanical stirrer was placed 59.6 g (0.22 mol) of phosphorus tribromide. The flask was immersed in an ice bath. Methacrylic acid (43 g, 0.5 mol) was gradually added to the stirred phosphorus tribromide through the dropping funnel over a period of 2 hours. The reaction mixture is stirred for a further 5 hours, during which time the temperature of the reaction mixture rose to approx. 40 °C. The mixture was then allowed to stand for 16 hours in a cooler at 8°C. The Fos acidification layer is separated from the methacrylyl bromide layer in a separatory funnel, and the latter is then distilled under reduced pressure. The yield of the main fraction boiling at 43.5-45.0°C at 40 mm Hg pressure was 32 g or 43 percent of theory.
B. Reaksjon av methacrylylbromid med epoxydisert sojabønneolje — Epoxydisert soja-bønneolje (30,5 g, 0,134 mol ethylenoxydoxygen) fortynnes med 15 g styren og 0,033 g hydrokinon. Den resulterende klare blanding opphetes til 98°C på et kokende vannbad. Methacrylylbromid (9,7 g, 0,065 mol) tilsettes gradvis til den om-rørte blanding av styren og epoxydisert sojabøn-neolje ved 98°C i løpet av H/2 time. Ved slutten av denne tid ble ethylenoxydoxygeninnholdet i reaksjonsblandingen redusert fra en opprinnelig verdi av 3,88 vektprosent til 1,24 vektprosent, syreverdien er 0,03 mekv/g, forsåpningstallet er 3,93 mekv/g og totalt brominnhold er 9,48 vektprosent. Styren (5 g) og benzoylperoxyd (0,97 g) tilsettes til reaksjonsblandingen som derpå stø-pes i en form, opphetes her i 16 timer ved 65— 68°C, fjernes fra formen og opphetes y2 time ved 125°C. Det resulterende sampolymer er seigt og fleksibelt, har en strekkstyrke av 126 kg/cm2 (1850 psi), en strekkmodul av 3522 kg/cm<2 >(50 100 psi), skjærmodul av 4,22 kg/cm? (5000 psi), skjærfasthet 146 kg/cm2 (2080 psi) og en Clash-Berg elastisitetsmodul T4-verdi av 38°C. B. Reaction of Methacrylyl Bromide with Epoxidized Soybean Oil — Epoxidized soybean oil (30.5 g, 0.134 mol ethyleneoxydoxygen) is diluted with 15 g of styrene and 0.033 g of hydroquinone. The resulting clear mixture is heated to 98°C on a boiling water bath. Methacrylyl bromide (9.7 g, 0.065 mol) is gradually added to the stirred mixture of styrene and epoxidized soybean oil at 98°C over 1/2 hour. At the end of this time, the ethyleneoxydoxygen content in the reaction mixture was reduced from an initial value of 3.88% by weight to 1.24% by weight, the acid value is 0.03 meq/g, the saponification number is 3.93 meq/g and the total bromine content is 9.48% by weight . Styrene (5 g) and benzoyl peroxide (0.97 g) are added to the reaction mixture, which is then poured into a mold, heated here for 16 hours at 65-68°C, removed from the mold and heated for 2 hours at 125°C. The resulting copolymer is tough and flexible, has a tensile strength of 126 kg/cm2 (1850 psi), a tensile modulus of 3522 kg/cm<2 >(50 100 psi), shear modulus of 4.22 kg/cm? (5000 psi), shear strength 146 kg/cm2 (2080 psi) and a Clash-Berg modulus of elasticity T4 value of 38°C.
Eksempel 63. Example 63.
Dette eksempel viser et nabo-acryloxy-klor-.sojabønneoljederivat fremstilt ved å la sojabøn-neolje reagere med acrylsyre og klor. En blanding av sojabønneolje (58,8 g, 0,30 mol vinyl-en umettethet), acrylsyre (43,2 g, 0,60 mol), calciumacrylat (27,3 g, 0,15 mol), tetramethylammoniumklorid (0,33 g, 0,003 mol) ble brakt til å reagere med klorgass (23,6 g, 0,33 mol) som langsomt ble tilsatt i løpet av 1% time og temperaturen ble holdt ved 30—35°C. Faststoff ble fjernet fra reaksjonsblandingen ved sentrifugering. Det klargjorte flytende materiale ble skilt i to lag, idet det nedre er høyviskost og inneholder oppløst calciumacrylat. Det øvre lag ble oppløst i ethylether og vasket gjentatte ganger med små porsjoner fortynnet vandig natriumcarbonat inntil det var befridd for syre, og derpå med destillert vann inntil det var fritt for carbonat. Det vaskede og tørkede oljeaktige produkt viste ved analyse ca. 90 pst. tap av opprinnelig vinyl-enumettethet, ca. 55 pst. omdannelse av de opprinnelige vinylengrupper til nabo-methacryloxy-klorgrupper og ca. 35 pst. ytterligere klorering av vinylengruppene. Sampolymerisering av 53 vektdeler av det vaskede og tørkede produkt med 33 vektdeler styren og 14 vektdeler acrylsyre under anvendelse av benzoylperoxydkatalysator, This example shows a neighboring acryloxy-chloro-soybean oil derivative prepared by reacting soybean oil with acrylic acid and chlorine. A mixture of soybean oil (58.8 g, 0.30 mol vinyl-one unsaturation), acrylic acid (43.2 g, 0.60 mol), calcium acrylate (27.3 g, 0.15 mol), tetramethylammonium chloride (0, 33 g, 0.003 mol) was reacted with chlorine gas (23.6 g, 0.33 mol) which was slowly added over 1% hour and the temperature was maintained at 30-35°C. Solids were removed from the reaction mixture by centrifugation. The prepared liquid material was separated into two layers, the lower one being highly viscous and containing dissolved calcium acrylate. The upper layer was dissolved in ethyl ether and washed repeatedly with small portions of dilute aqueous sodium carbonate until free of acid, and then with distilled water until free of carbonate. The washed and dried oily product showed on analysis approx. 90 percent loss of original vinyl monosaturation, approx. 55 percent conversion of the original vinylene groups into neighboring methacryloxy chlorine groups and approx. 35 percent further chlorination of the vinylene groups. Copolymerization of 53 parts by weight of the washed and dried product with 33 parts by weight of styrene and 14 parts by weight of acrylic acid using benzoyl peroxide catalyst,
gav et klart, gult, elastisk fast materiale med gave a clear, yellow, elastic solid material with
god styrke. good strength.
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IT4962576A IT1069068B (en) | 1976-05-24 | 1976-05-24 | Grain oriented silicon steel annealing separator - based on magnesium oxide and contg. rare earth oxides or metal silicates |
IT49142/77A IT1116431B (en) | 1977-04-27 | 1977-04-27 | ANNEALING SEPARATOR |
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JP4585101B2 (en) * | 2000-08-25 | 2010-11-24 | 新日本製鐵株式会社 | Low noise transformer electrical steel sheet |
CN101180411B (en) | 2005-05-23 | 2012-01-11 | 新日本制铁株式会社 | Grain oriented electromagnetic steel sheet having excellent film adhesion and process for producing the same |
KR101165430B1 (en) * | 2006-11-22 | 2012-07-12 | 신닛뽄세이테쯔 카부시키카이샤 | Unidirectionally grain oriented electromagnetic steel sheet having excellent film adhesion, and method for manufacturing the same |
KR101762341B1 (en) * | 2015-12-18 | 2017-07-27 | 주식회사 포스코 | Annealing separating agent for oriented electrical steel, oriented electrical steel, and method for manufacturing oriented electrical steel |
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US3389006A (en) | 1964-05-18 | 1968-06-18 | Armco Steel Corp | Process for forming a refractory coating on silicon-iron stock |
US3333992A (en) | 1964-06-29 | 1967-08-01 | Armco Steel Corp | Production of oriented silicon-iron using grain growth inhibitor during primary recrystallization heat treatment |
US3379581A (en) * | 1964-12-21 | 1968-04-23 | Armco Steel Corp | Desulfurizing coating for ferrous material and method of using it |
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US3868280A (en) | 1967-12-12 | 1975-02-25 | Takaaki Yamamoto | Method of forming electric insulating films oriented silicon steel |
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FR2352888A1 (en) | 1977-12-23 |
DD130664A5 (en) | 1978-04-19 |
RO71135A (en) | 1981-09-24 |
GB1563853A (en) | 1980-04-02 |
HU181650B (en) | 1983-10-28 |
BE854833A (en) | 1977-09-16 |
NO147035C (en) | 1983-01-19 |
CS207458B1 (en) | 1981-07-31 |
LU77395A1 (en) | 1977-08-29 |
BG39978A3 (en) | 1986-09-15 |
SE7706015L (en) | 1977-11-25 |
NL7705718A (en) | 1977-11-28 |
FR2352888B1 (en) | 1980-02-15 |
ES459101A1 (en) | 1978-11-01 |
JPS6115152B2 (en) | 1986-04-22 |
DE7716282U1 (en) | 1984-05-24 |
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NO771781L (en) | 1977-11-25 |
PL198370A1 (en) | 1978-01-30 |
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