JPH01297411A - Copolymer of alkenyl ether with maleic anhydride - Google Patents
Copolymer of alkenyl ether with maleic anhydrideInfo
- Publication number
- JPH01297411A JPH01297411A JP63125014A JP12501488A JPH01297411A JP H01297411 A JPH01297411 A JP H01297411A JP 63125014 A JP63125014 A JP 63125014A JP 12501488 A JP12501488 A JP 12501488A JP H01297411 A JPH01297411 A JP H01297411A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- copolymer
- maleic anhydride
- alkenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 alkenyl ether Chemical compound 0.000 title claims abstract description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229920001577 copolymer Polymers 0.000 title claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000003628 tricarboxylic acids Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006227 byproduct Chemical class 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- IBFJDBNISOJRCW-UHFFFAOYSA-N 3-methylphthalic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C(O)=O IBFJDBNISOJRCW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 1
- VTDOEFXTVHCAAM-UHFFFAOYSA-N 4-methylpent-3-ene-1,2,3-triol Chemical compound CC(C)=C(O)C(O)CO VTDOEFXTVHCAAM-UHFFFAOYSA-N 0.000 description 1
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- QWIZNVHXZXRPDR-UHFFFAOYSA-N D-melezitose Natural products O1C(CO)C(O)C(O)C(O)C1OC1C(O)C(CO)OC1(CO)OC1OC(CO)C(O)C(O)C1O QWIZNVHXZXRPDR-UHFFFAOYSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- MUPFEKGTMRGPLJ-OBAJZVCXSA-N Gentianose Natural products O(C[C@@H]1[C@@H](O)[C@H](O)[C@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@H](O)[C@@H](CO)O2)O1)[C@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-OBAJZVCXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
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- 229930195725 Mannitol Natural products 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 239000002738 chelating agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
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- 229940009714 erythritol Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- MUPFEKGTMRGPLJ-WSCXOGSTSA-N gentianose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-WSCXOGSTSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- QWIZNVHXZXRPDR-WSCXOGSTSA-N melezitose Chemical compound O([C@@]1(O[C@@H]([C@H]([C@@H]1O[C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)O)CO)CO)[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O QWIZNVHXZXRPDR-WSCXOGSTSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical compound CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HSBSUGYTMJWPAX-HNQUOIGGSA-N trans-2-hexenedioic acid Chemical compound OC(=O)CC\C=C\C(O)=O HSBSUGYTMJWPAX-HNQUOIGGSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1441—Monomers containing side chains of polypropylene oxide groups
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は分子内にカルボキシル基を含有するポリオキシ
アルキレンポリオールモノアルケニルエーテルと無水マ
レイン酸との新規な共重合体に関するもので２反応性被
覆材料、たんばく質の修飾剤などとして利用することが
できる。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel copolymer of a polyoxyalkylene polyol monoalkenyl ether containing a carboxyl group in the molecule and maleic anhydride, and is a two-reactive coating. It can be used as a material, protein modifier, etc.
ポリオキシアルキレングリコールモノアリルエーテルと
マレイン酸系単量体との共重合体は、特開昭５９−１７
６３１２号公報等に開示され、スケール防止剤、キレー
ト剤２分散剤などとして使用される。A copolymer of polyoxyalkylene glycol monoallyl ether and maleic acid monomer is disclosed in JP-A-59-17
It is disclosed in Japanese Patent No. 6312, etc., and is used as a scale inhibitor, chelating agent, dispersant, etc.
前記の公報に開示された共重合体は、ポリオキシアルキ
レングリコールモノアリルエーテルとマレイン酸または
無水マレイン酸とを水溶液中で共重合させて得られるも
ので、その実施例によると数平均分子量は９５０〜１２
５０と低い。また。The copolymer disclosed in the above publication is obtained by copolymerizing polyoxyalkylene glycol monoallyl ether and maleic acid or maleic anhydride in an aqueous solution, and according to the examples, the number average molecular weight is 950. ~12
It's as low as 50. Also.
共重合体中のポリオキシアルキレングリコール鎖の太端
が水酸基であるため、共重合体中のカルボキシル基含有
量も低かった。そのため、共重合体中のカルボキシル基
を用いてたんばく質などの修飾を充分におこなうことが
できなかった。Since the thick end of the polyoxyalkylene glycol chain in the copolymer was a hydroxyl group, the content of carboxyl groups in the copolymer was also low. Therefore, it has not been possible to sufficiently modify proteins and the like using the carboxyl groups in the copolymer.
本発明は特定のアルケニル基とカルボキシル基を含有す
るポリオキシアルキレンポリオールモノアルケニルエー
テル（以下、単にアルケニルエーテルという。）と無水
マレイン酸との共重合体を目的とするもので、より高分
子量、かつカルボキシル基含有量の高い共重合体である
。The present invention aims at a copolymer of polyoxyalkylene polyol monoalkenyl ether (hereinafter simply referred to as alkenyl ether) containing specific alkenyl groups and carboxyl groups and maleic anhydride, which has a higher molecular weight and It is a copolymer with a high content of carboxyl groups.
〔課題を解決するための手段〕
本発明は一般式（１）で示されるアルケニルエーテルと
無水マレイン酸との共重合体で、必要によシさらに他の
単量体との共重合体であり、アルケニルエーテルと無水
マレイン酸と他の単量体とのモル比が５〜６０：４０〜
７０：０〜４０である共重合体である。[Means for Solving the Problems] The present invention is a copolymer of an alkenyl ether represented by the general formula (1) and maleic anhydride, optionally with other monomers. , the molar ratio of alkenyl ether to maleic anhydride to other monomers is 5 to 60:40 to
It is a copolymer with a ratio of 70:0 to 40.
（ただし、Ｂは２〜８個の水酸基を持つ化合物の残基、
ＡＯは炭素数２〜１８のオキシアルキレン基の１種また
は２種以上の混合物で、２種以上のときはブロック状に
付加していてもランダム状に付加していてもよく、Ｘは
炭素数２〜５のアルケニル基、Ｙはジカルボン酸または
トリカルボン酸のアシル基、または炭素数１〜３のアル
キレン基を表わし、Ｒは炭素数１〜２４の炭化水素基、
１≦ａ≦７．０≦ｂ≦６．０≦Ｃ≦６．かつ１≦ａ＋ｌ
）＋ｃ≦７であり、に、！、ｍ、ｎはオキシアルキレ／
基の平均付加モル数でそれぞれ０〜１０００、かつに＋
ａノ＋ｂ ｍ ＋ ｃ ｎ ＝ １〜３０００ 。(However, B is a residue of a compound having 2 to 8 hydroxyl groups,
AO is one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 18 carbon atoms, and when there are two or more kinds, they may be added in a block shape or in a random shape, and X is the number of carbon atoms. 2-5 alkenyl group, Y represents an acyl group of dicarboxylic acid or tricarboxylic acid, or an alkylene group having 1-3 carbon atoms, R is a hydrocarbon group having 1-24 carbon atoms,
1≦a≦7.0≦b≦6.0≦C≦6. and 1≦a+l
)+c≦7, and! , m, n are oxyalkylene/
The average number of moles added of the group is 0 to 1000, and +
a no + b m + c n = 1 to 3000.
ｐは１または２である。）
一般式（１）において、Ｂで示される２〜８個の水酸基
を持つ化合物としては、エチレングリコール、プロピレ
ングリコール、フチレンクリコール、ヘキシレングリコ
ール、スチレングリコール。p is 1 or 2. ) In the general formula (1), the compound having 2 to 8 hydroxyl groups represented by B includes ethylene glycol, propylene glycol, ethylene glycol, hexylene glycol, and styrene glycol.
炭素数８〜１８のアルキレングリコール、ネオペンチル
グリコールなどのグリコール類、グリセリフ、ト＋）メ
チロールエタン、トリメチロールプロパン、１，３．５
−ペンタントリオール、エリスリトール、ペンタエリス
リトール、ジペンタエリスリトール、ソルビトール、ソ
ルビタン、ソルバイト、ソルビトールとグリセリンの縮
合物、アドニトール、アラヒト−ルウキシリトール、マ
ンニトールなどの多価アルコール類、あるいはそれらの
部分エーテル化物またはエステル化物、キシロース、ア
ラビノース、リボース、ラムノーズ、グルコース、フル
クトース、ガラクトース、マンノース、ソルボース、セ
ロビオース、マルトース。Glycols such as alkylene glycols having 8 to 18 carbon atoms and neopentyl glycol, glycols, trimethylolethane, trimethylolpropane, 1,3.5
- Polyhydric alcohols such as pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbite, condensates of sorbitol and glycerin, adonitol, arachyto-ruuxylitol, mannitol, or partially etherified or esterified products thereof , xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose.
イソマルトース、トレハロース、シュークロース。isomaltose, trehalose, sucrose.
ラフィノース、ゲンチアノース、メレジトースなどの糖
類あるいはそれらの部分エーテル化物またはエステル化
物、カテコール、レゾルシノール。Saccharides such as raffinose, gentianose, melezitose or their partially etherified or esterified products, catechol, resorcinol.
ヒドロキノン、フロログルシンなどのフェノール類があ
げられる。ＡＯで示される炭素数２〜１８のオキシアル
キレン基としては、オキシエチレン基、オキシプロピレ
ン基、オキシブチレン基、オキシテトラメチレン基、オ
キシスチレン基、オキシドデシレン基、オキシテトラデ
シレン基、オキシヘキサデシレン基、オキシオクタデシ
レン基などがある。Ｘで示される炭素数２〜５のアルケ
ニル基としては、ビニル基、アリル基、メタリル基。Examples include phenols such as hydroquinone and phloroglucin. The oxyalkylene group having 2 to 18 carbon atoms represented by AO includes oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group, oxystyrene group, oxidedecylene group, oxytetradecylene group, oxyhexane group. Examples include decylene group and oxyoctadecylene group. The alkenyl group having 2 to 5 carbon atoms represented by X includes a vinyl group, an allyl group, and a methallyl group.
１．１−ジメチル−２−プロペニル基、３−メｆルー３
−ブテニル基などがある。一般式（１）のＹをアシル残
基とするジカルボン酸あるいはトリカルボン酸としては
、シチ、マロン酸、コハク酸、グルタル酸、アジピン酸
、ピメリン酸、スペリン酸、アゼライン酸、セパシン酸
、ウンデカン二酸、ドデカンニ酸、ブラシリン酸、テト
ラデカンニ酸、ペンタデカンニ酸、タブシン酸、ヘプタ
デカンニ酸、オクタデカンニ酸、ノナデカンニ酸。1.1-dimethyl-2-propenyl group, 3-metyl group
-butenyl group, etc. Dicarboxylic acids or tricarboxylic acids in which Y in general formula (1) is an acyl residue include citrate, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sepacic acid, and undecanedioic acid. , dodecanoic acid, brassicic acid, tetradecanoic acid, pentadecanoic acid, tabucic acid, heptadecanonic acid, octadecanoic acid, nonadecanonic acid.
アイコサンニ酸、などの飽和ジカルボン酸類、マレイン
酸、フマル酸、イタコン酸、シトラコン酸。Saturated dicarboxylic acids such as icosanniic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
メサコン酸、クスグルタコン酸、トランスグルタコン酸
、α−ジヒドロムコン酸、β−ジヒドロムコン酸などの
不飽和ジカルボン酸類、トリカルバリル酸、クエン酸な
どのトリカルボン酸類、リンコ酸、酒石酸などのヒドロ
キシカルボン酸類、フメル酸、イソフタル酸、テレフタ
ル酸、３−メチルフタル酸、４−メチルフタル酸、２−
メチルインフタル酸、４−メチルイソフタル酸、メチル
テンゼントリカルボン酸類があげられる。またＹが炭素
数１〜３のアルキレン基を表わすときには。Unsaturated dicarboxylic acids such as mesaconic acid, cusglutaconic acid, transglutaconic acid, α-dihydromuconic acid, and β-dihydromuconic acid, tricarboxylic acids such as tricarballylic acid and citric acid, hydroxycarboxylic acids such as linchoic acid and tartaric acid, and fumeric acid. , isophthalic acid, terephthalic acid, 3-methylphthalic acid, 4-methylphthalic acid, 2-
Examples include methylinphthalic acid, 4-methylisophthalic acid, and methyltenzenetricarboxylic acids. Further, when Y represents an alkylene group having 1 to 3 carbon atoms.
メチレン基、エチレン基、エチリデン基、プロピリデン
基、インプロピリデン基などである。Ｒで示される炭素
数１〜２４の炭化水素基としては。These include methylene group, ethylene group, ethylidene group, propylidene group, and inpropylidene group. The hydrocarbon group having 1 to 24 carbon atoms represented by R is as follows.
メチル基、エチル基、アリル基、プロピル基、インプロ
ピル基、ブチル基、イソブチル基、ターシャリブチル基
、アミル基、インアミル基、ヘキシル基、ヘプチル基、
２−エチルヘキシル基、オクチル基、ノニル基、デシル
基、ウンデシル基、ドデシル基、トリデンル基、テトラ
デシル基、ヘキサデシル基、インヘキサデシル基、オク
タデシル基、インオクタデシル基、オレイル基、オクチ
ルドデシル基、ヘヘニル基、テシルテトラデシル基。Methyl group, ethyl group, allyl group, propyl group, inpropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, inamyl group, hexyl group, heptyl group,
2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridenyl group, tetradecyl group, hexadecyl group, inhexadecyl group, octadecyl group, inoctadecyl group, oleyl group, octyldodecyl group, hehenyl group , tesyltetradecyl group.
ベンジル基、クレジル基、ブチルフェニル基、ジブチル
フェニル基、オクチルフェニ／１／基、 ／ニルフェニ
ル基、ドデシルフェニル基、ジオクチルフェニル基、ジ
ノニルフェニル基、スチレン化フェニル基などである。Examples include benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylpheny/1/ group, /nylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, and styrenated phenyl group.
本発明で用いる一般式（１）のアルケニルエーテルは種
々の方法で製造することができるが、つぎに代表例を示
す。The alkenyl ether of general formula (1) used in the present invention can be produced by various methods, and representative examples are shown below.
（ａ） Ｂを残基とする多価アルコール、多価フェノ
ールまたは糖類に炭素数２〜１８のアルキレンオキシド
を付加反応させ、ついで炭素数２〜５ノハロケン化アル
ケニルを反応させる。つぎに必要に応じてハロゲン化ア
ルキルを反応させたのち。(a) An alkylene oxide having 2 to 18 carbon atoms is added to a polyhydric alcohol, a polyphenol, or a saccharide having B as a residue, and then a halokenyl alkenyl having 2 to 5 carbon atoms is reacted. Next, if necessary, after reacting with an alkyl halide.
ジカルボン酸またはトリカルボン酸またはそれらの酸無
水物を反応させてエステル化物とするか。Will dicarboxylic acids, tricarboxylic acids, or their acid anhydrides be reacted to form esters?
あるいは下記一般式（２）で示されるアルキルカルボン
酸のモノハロゲン置換体とのウィリアムノン合成反応を
行なうことによりエーテル化物とする。Alternatively, an etherified product is obtained by carrying out a Williamnon synthesis reaction with a monohalogen-substituted alkylcarboxylic acid represented by the following general formula (2).
Ｚ −Ｒｚ −ＣＯＯＨ・・・・・・・・・・・・・・
・（２）（ただし、２は塩素原子または臭素原子であり
。Z -Rz -COOH・・・・・・・・・・・・・・・
・(2) (However, 2 is a chlorine atom or a bromine atom.
Ｒ２は一般式（１）におけるＹが炭素数１〜３のアルキ
レン基を表わすときと同一である。）（ｂ） 炭素数
２〜５のアルケニルアルコールに炭素数２〜１８のアル
キレンオキシドを付加反応させる。つぎにジカルボン酸
またはトリカルボン酸またはそれらの酸無水物を反応さ
せてエステル化物とするか、あるいは一般式（２）で示
されるアルキルカルボン酸のモノハロゲン置換体トのウ
ィリアムノン合成反応を行なうことによりエーテル化物
とする。R2 is the same as in general formula (1) when Y represents an alkylene group having 1 to 3 carbon atoms. )(b) An alkenyl alcohol having 2 to 5 carbon atoms is subjected to an addition reaction with an alkylene oxide having 2 to 18 carbon atoms. Next, by reacting dicarboxylic acid or tricarboxylic acid or their acid anhydrides to form an ester, or by carrying out a Williamone synthesis reaction of a monohalogen-substituted alkylcarboxylic acid represented by general formula (2). Make it into an ether.
（ｃ） 炭素数２〜５のアルケニルアルコールにグリ
シドールを付加させたのち、炭素数２〜１８のアルキレ
ンオキシドを付加反応させる。つぎに必要に応じてハロ
ゲン化アルキルを反応させたのち、ジカルボン酸または
トリカルボン酸またはそれらの酸無水物を反応させてエ
ステル化物とするか、あるいは一般式（２）で示される
アルキルカルボン酸のモノハロゲン置換体とのウィリア
ムノン合成反応を行なうことによりエーテル化物とする
。(c) Glycidol is added to an alkenyl alcohol having 2 to 5 carbon atoms, and then an alkylene oxide having 2 to 18 carbon atoms is subjected to an addition reaction. Next, if necessary, after reacting with an alkyl halide, a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof is reacted to obtain an ester, or a monomer of the alkylcarboxylic acid represented by the general formula (2) is prepared. An etherified product is obtained by carrying out a Williamnon synthesis reaction with a halogen-substituted product.
（ｄ） 炭素数１〜２４のアルコールにグリシドール
を付加させたのち、炭素数２〜１８のアルキレンオキシ
ドを付加反応させる。つぎにハロゲン化アルキルを反応
させたのち、ジカルボン酸またはトリカルボン酸または
それらの酸無水物を反応させてエステル化物とするか、
あるいは一般式（２）に示されるアルキルカルボン酸の
モノハロゲン置換体とウィリアムノン合成を行なうこと
によりエーテル化物とする。(d) After adding glycidol to an alcohol having 1 to 24 carbon atoms, an alkylene oxide having 2 to 18 carbon atoms is subjected to an addition reaction. Next, after reacting the alkyl halide, dicarboxylic acid or tricarboxylic acid or their acid anhydrides are reacted to form an ester, or
Alternatively, an etherified product is obtained by performing Williamnon synthesis with a monohalogen-substituted alkylcarboxylic acid represented by the general formula (2).
他の単量体としては一般式（１）のアルケニルエーテル
および無水マレイン酸と共重合しうるビニル型単量体で
あり、アクリル酸、メタクリル酸。Other monomers include alkenyl ethers of general formula (1) and vinyl monomers copolymerizable with maleic anhydride, such as acrylic acid and methacrylic acid.
イタコン酸、クロトン酸、マレイン酸、これらの１価ま
たは２価の金属塩、アンモニウム塩、有機アンモニウム
塩、炭素数１〜２４のアルコールとのエステル化物、さ
らにはスチレン、メチルスチレンなどの芳香族ビニル化
合物、塩化ビニル、塩化ビニリデンなどのハロゲン化ビ
ニル化合物、インブチレン、ジイソブチレンなどのオレ
フィン類。Itaconic acid, crotonic acid, maleic acid, monovalent or divalent metal salts, ammonium salts, organic ammonium salts, esterified products with alcohols having 1 to 24 carbon atoms, and aromatic vinyls such as styrene and methylstyrene. compounds, vinyl chloride, vinyl halide compounds such as vinylidene chloride, and olefins such as imbutylene and diisobutylene.
酢酸ビニル、アクリロニトリル、アクリルアミドなどで
ある。These include vinyl acetate, acrylonitrile, and acrylamide.
本発明の共重合体は、一般式（１）のアルケニルエーテ
ルと無水マレイン酸とを、必要により他の単量体を加え
７重合開始剤の存在下に塊状重合。The copolymer of the present invention is obtained by bulk polymerizing the alkenyl ether of the general formula (1) and maleic anhydride in the presence of a polymerization initiator, adding other monomers as necessary.
溶液重合などの方法により共重合させて得られる。It is obtained by copolymerization using methods such as solution polymerization.
重合開始剤としては、ベンゾイルペルオキシド。Benzoyl peroxide is used as a polymerization initiator.
ラウロイルペルオキシド、ジターシャリブチルペルオキ
シドなどの有機過酸化物、アゾビスイソブチロニトリル
などのアゾ化合物等がある。Examples include organic peroxides such as lauroyl peroxide and di-tert-butyl peroxide, and azo compounds such as azobisisobutyronitrile.
溶液重合に用いる溶媒としては、ベンゼン、トルエン、
キシレンなどの芳香族炭化水素、ｎ−ヘキサン、シクロ
ヘキサンなどの脂肪族炭化水素。Solvents used for solution polymerization include benzene, toluene,
Aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as n-hexane and cyclohexane.
アセトン、メチルエチルケトンなどのケトン、ジメチル
エーテル、ジエチルエーテル、テトラヒドロフラン、ジ
オキサンなどのエーテル、クロロホルム、四塩化炭素な
どのハロゲン化炭化水素等がある。Examples include ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
本発明の共重合体は、一般式（１）のアルケニルエーテ
ルの選定９重合反応における溶媒の選定等により、液体
状、ゲル状または固体状の、あるいは親水性または疎水
性の２種々の性状のものとして得ることが可能である。The copolymer of the present invention can have various properties such as liquid, gel, or solid, or hydrophilic or hydrophobic, depending on the selection of the alkenyl ether of general formula (1) and the selection of the solvent in the polymerization reaction. It is possible to obtain it as such.
たとえば、溶液重合においてアルケニルエーテルの５倍
重量以上の溶媒を用い、アルケニルエーテルがオキシエ
チレン基を含有しないかあるいはごくわずかしか含有し
ないもので２分子量２０００以上のものを用いれば液体
状の共重合体が得られ、アルケニル基がメタリル基から
なる分子量２０００以下のものを用いればゲル状の共重
合体が得られる。また、ポリオキンアルキレン基がポリ
オキシエチレン基からなる分子（ｉ ２０００以上のア
ルケニルエーテルを用いると固体の共重合体が得られる
。また、オキシエチレン基の含有量の大きいアルケニル
エーテルを用いれば親水性の共重合体が得られ、オキシ
エチレン基の含有量の小さいものを用いれば疎水性の共
重合体が得られる。For example, in solution polymerization, if a solvent with a weight of at least 5 times that of the alkenyl ether is used, and the alkenyl ether contains no or only a small amount of oxyethylene group and has a molecular weight of 2,000 or more, a liquid copolymer can be obtained. A gel-like copolymer can be obtained by using a copolymer having a molecular weight of 2,000 or less, in which the alkenyl group is a methallyl group. In addition, a solid copolymer can be obtained by using an alkenyl ether in which the polyoxyethylene group is a polyoxyethylene group (i 2000 or more).In addition, if an alkenyl ether with a large content of oxyethylene groups is used, a hydrophilic copolymer can be obtained. If a copolymer with a small content of oxyethylene groups is used, a hydrophobic copolymer can be obtained.
本発明は、一般式（１）の分子内にカルボキシル基を含
有するアルケニルエーテルと無水マレイン酸を必須成分
としたことにより、比較的高分子食かつカルボキシル基
含有量の高い共重合体が。The present invention provides a copolymer with a relatively high molecular weight and high carboxyl group content by using an alkenyl ether containing a carboxyl group in the molecule of general formula (1) and maleic anhydride as essential components.
液体状、ゲル状、固体状あるいは親水性、疎水性のいず
れの性状のものでも自由に得ることができる。このため
、今までスケール防止剤などのごく限られた利用範囲し
かなかったアルケニルエーテ〔実施例〕
以下にアルケニルエーテルの製造例、実施例により本発
明を説明する。It can be freely obtained in any of liquid, gel, solid, hydrophilic, and hydrophobic forms. For this reason, alkenyl ethers have hitherto been used only in a very limited range as scale inhibitors [Examples] The present invention will be explained below with reference to production examples and examples of alkenyl ethers.
製造例１
加圧反応器にアリルアルコール５８ｙ′と水酸化カリウ
ム５２を入れ、窒素雰囲気下、１１０〜１２０℃、圧力
０．５〜３ Ｋｇ ／ ｃＡ （ゲージ圧、以下間シ。Production Example 1 Allyl alcohol 58y' and potassium hydroxide 52 were placed in a pressurized reactor, and the temperature was 110-120°C under a nitrogen atmosphere at a pressure of 0.5-3 Kg/cA (gauge pressure, below).
）でプロピレンオキシド１．５５ Ｏｆを徐々に圧入し
ながら付加反応を行なった。反応終了後。), the addition reaction was carried out while gradually pressurizing 1.55 Of of propylene oxide. After the reaction is complete.
水酸化カリウムを塩酸で中和し、副生じた塩をろ過によ
り除いた。得られたポリオキシプロピレングリコールモ
ノアリルエーテルの水酸基価は４０゜１であった。Potassium hydroxide was neutralized with hydrochloric acid, and by-product salts were removed by filtration. The obtained polyoxypropylene glycol monoallyl ether had a hydroxyl value of 40°1.
得られた生成物７００２とモノクロロ酢酸５７１を加圧
反応器に入れ、窒素雰囲気下、１００〜１１０℃に加熱
し、９Ｎ水酸化ナトリウム水溶液１００ｍ／を徐々に圧
入した。全量圧入後、温度を１２０〜１４０℃に制御し
、５時間反応を行なった。ついで９Ｎの塩酸水溶液１５
０ゴを入れ、９０〜１１０℃で１時間処理後、１ノの飽
和食塩水で５回水洗を行なった。１１０±１０℃、１０
〜３０ ｍｍ ／Ｈｆの減圧下で脱水後、生成する塩を
ろ過により除き、５５０ｆのアルケニルエーテルをｉた
。エーテル化率は９５．１％であった。The obtained product 7002 and monochloroacetic acid 571 were placed in a pressurized reactor, heated to 100 to 110° C. under a nitrogen atmosphere, and 100 m/a of 9N aqueous sodium hydroxide solution was gradually introduced under pressure. After the entire amount was injected, the temperature was controlled at 120 to 140°C, and the reaction was carried out for 5 hours. Then 9N hydrochloric acid aqueous solution 15
After treatment at 90 to 110° C. for 1 hour, the mixture was washed 5 times with 1 ml of saturated saline. 110±10℃, 10
After dehydration under reduced pressure of ~30 mm/Hf, the resulting salts were removed by filtration to yield 550f alkenyl ether. The etherification rate was 95.1%.
製造例２
加圧反応器にメタリルアルコール７２ｙと水酸化カリウ
ム５．６２を入れ、窒素雰囲気下、１００〜１２０℃、
圧力０ 、５〜３ Ｋｇ／ ｃｒＡでエチレンオキシド
９２５ｆｉ’とプロピレンオキシド１２２Ｏｒの混合物
を徐々に圧入しながら付加反応を行なった。反応終了後
、水酸化カリウムを塩酸で中和し。Production Example 2 Methallyl alcohol 72y and potassium hydroxide 5.62% were placed in a pressurized reactor, and heated at 100 to 120°C under a nitrogen atmosphere.
An addition reaction was carried out while gradually pressurizing a mixture of 925 fi' of ethylene oxide and 122 Or of propylene oxide at a pressure of 0 and 5 to 3 Kg/crA. After the reaction is complete, neutralize potassium hydroxide with hydrochloric acid.
副生じた塩をろ過により除いた。得られたポリオキ／エ
チレンポリオキシプロピレングリコールモノメタリルエ
ーテルの水酸基価は２９．５であった。By-product salts were removed by filtration. The obtained polyoxy/ethylene polyoxypropylene glycol monometallyl ether had a hydroxyl value of 29.5.
得られた生成物９５０グと無水コノ＼り酸５２゜５１ｉ
＋およびトリエチルアミン５０．６Ｓ’を還流装置、窒
素ガス吹き込み管、温度計、攪拌装置を取り付けた四つ
ロフラスコに入れ、窒素気流下、１００±５℃で３時間
攪拌を行なった。ついでトリエチルアミンを２〜５ ｍ
ｍ ／Ｈ！Ｆの減圧下、１３０士５℃で除去し、ポリオ
キシエチレンポリオキシプロピレングリコールモノメタ
リルエーテルのモノコ・・り酸エステル９６０７を得た
。エステル化率は９２．２チであった。950 grams of the obtained product and 52.51 grams of phosphoric anhydride
+ and triethylamine 50.6S' were placed in a four-loaf flask equipped with a reflux device, a nitrogen gas blowing tube, a thermometer, and a stirring device, and stirred at 100±5° C. for 3 hours under a nitrogen stream. Then add 2 to 5 m of triethylamine.
m/H! The residue was removed under reduced pressure at 130 °C and 5°C to obtain monoco-phosphate ester 9607 of polyoxyethylene polyoxypropylene glycol monometallyl ether. The esterification rate was 92.2.
製造例３
加圧反応器にイソプロピリデングリセロール１３２２、
水酸化カリウム２２を入れ、窒素雰囲気下、１２０〜１
３０℃、圧力０．５〜３に９／ｃｄでエチレンオキシド
４５０グを徐々に圧入しながら付加反応を行なった。反
応終了後、水酸化カリウム６０２を入れ、窒素雰囲気下
、１１０〜１２０℃、圧力０ 、５〜３ Ｋｇ／ ｃｔ
Ａでアリルクロリド９０１を徐々に加えて反応を行ない
、４時間経過後反応混合物のアルカリ度が減少してほぼ
一定の値となったので反応を止め、トルエン６００１を
加えたのち、イオン交換水４００？にて３回水洗を行な
った。ついで２Ｎ塩酸水溶液によりｐＨを２以下とし、
８０℃で１時間窒素バブリングを行なった。ついで２Ｎ
水酸化す） ＩＪウム水溶液によりｐ″Ｈを７に調整し
、１１０±１０℃、２０〜５０咽Ｈ２の条件で２時間減
圧脱水を行なった。生成した塩をろ過により除去し、ポ
リオキシエチレングリコールモノアリルモノグリセロー
ルエーテルを得た。Production Example 3 Isopropylidene glycerol 1322 in a pressurized reactor,
Add 22% potassium hydroxide, under nitrogen atmosphere, 120~1
An addition reaction was carried out at 30° C. and a pressure of 0.5 to 3 while gradually pressurizing 450 g of ethylene oxide at a rate of 9/cd. After completion of the reaction, add potassium hydroxide 602, under nitrogen atmosphere, 110-120°C, pressure 0, 5-3 Kg/ct.
In step A, allyl chloride 901 was gradually added to carry out the reaction, and after 4 hours, the alkalinity of the reaction mixture decreased and reached a nearly constant value, so the reaction was stopped, and toluene 6001 was added, followed by 400 g of ion-exchanged water. ? Washed with water three times. Then, the pH was adjusted to 2 or less with a 2N aqueous hydrochloric acid solution,
Nitrogen bubbling was performed at 80° C. for 1 hour. Then 2N
The p″H was adjusted to 7 with an aqueous solution of hydroxide, and dehydration was performed under reduced pressure for 2 hours at 110±10°C and 20 to 50 H2.The generated salts were removed by filtration, and polyoxyethylene Glycol monoallyl monoglycerol ether was obtained.
水酸基価は１９６．５であった。The hydroxyl value was 196.5.
この生成物３４３．２５’と金属ナトリウム２８１を加
圧反応器に入れ、５０重量％モノクロロ酢酸ナトリウム
水溶液を、窒素雰囲気下１１０±１０℃の温度範囲にて
徐々に圧入した。全量圧入後。This product 343.25' and metallic sodium 281 were placed in a pressurized reactor, and a 50% by weight aqueous sodium monochloroacetate solution was gradually injected under nitrogen atmosphere at a temperature range of 110±10°C. After press-fitting the entire amount.
さらに１２０±１０℃で４時間反応を続けた。反応終了
後、５Ｎ塩酸水溶液によりｐＨ１に調整したのち、トル
エン７００？を加えて均一になるまで攪拌した。ついで
イオン交換水３００７を用いて水洗を３回行ない、１１
０±１０℃、２０〜５０咽Ｈ１で３時間脱水、脱トルエ
ンを行なった。生成した塩をろ過により除去し、２２０
Ｓｉ’のアリルエーテルを得た。エーテル化率は４５．
１％であった。The reaction was further continued for 4 hours at 120±10°C. After the reaction was completed, the pH was adjusted to 1 with a 5N aqueous hydrochloric acid solution, and then toluene was added to 700 ml of toluene. was added and stirred until uniform. Next, washing was performed three times using ion exchange water 3007, and 11
Dehydration and toluene removal were performed for 3 hours at 0±10° C. and 20 to 50 degrees H1. The generated salts were removed by filtration, and 220
Allyl ether of Si' was obtained. The etherification rate is 45.
It was 1%.
以下製造例１〜３と同様の方法により製造例４〜７のア
リルエーテルを得た。Allyl ethers of Production Examples 4 to 7 were obtained in the same manner as in Production Examples 1 to 3.
製造例１〜７で得たアルケニルエーテルの構造と分析結
果を表１に示す。Table 1 shows the structures and analysis results of the alkenyl ethers obtained in Production Examples 1 to 7.
一般式（１）のアルケニルエーテルを用いて本発明の重
合体を製造した。なお９重量平均分子量ハケルバーミニ
ニージョンクロマトクラフィーにより求めた。A polymer of the present invention was produced using an alkenyl ether of general formula (1). Note that the weight average molecular weight was determined by Hakelver mini-knee chromatography.
実施例１
下記の成分を冷却管、窒素ガス吹きこみ管、温度計およ
び攪拌器を備えた四つロフラスコに入れ。Example 1 The following ingredients were placed in a four-hole flask equipped with a cooling tube, nitrogen gas blowing tube, thermometer, and stirrer.
窒素気流下で８０℃に昇温し、４時間攪拌することＫよ
り共重合反応を行なった。The copolymerization reaction was carried out by raising the temperature to 80°C under a nitrogen stream and stirring for 4 hours.
製造例１のアルケニルエーテル
４６９．３Ｓ’（０，３モル）
無水マレイン酸 ２９．４９（０，３モル）ベンゾイ
ルペルオキシド
５２（単量体の１重量％）
トルエン ４９９Ｆ（単量体と同重量）ついで系
内温度を６０℃に冷却したのち、ぺ／シイルベルオキシ
ド５２を追加し、再度８０℃に昇温、４時間重合反応（
後重合）を行なった。反応終了後約１０ ｔａｎ ＨＰ
の減圧下に１１０℃でトルエンを留去して透明な粘性液
体である共重合体４９０２を得た。Alkenyl ether of Production Example 1 469.3S' (0.3 mol) Maleic anhydride 29.49 (0.3 mol) Benzoyl peroxide 52 (1% by weight of monomer) Toluene 499F (same weight as monomer) Then, after cooling the system temperature to 60°C, pe/silberoxide 52 was added, the temperature was raised to 80°C again, and the polymerization reaction (
Post-polymerization) was carried out. Approximately 10 tan HP after completion of reaction
Toluene was distilled off at 110° C. under reduced pressure to obtain copolymer 4902, which was a transparent viscous liquid.
共重合体の分析値
元素分析 Ｃ：（実測値）６０．５２％（計算値）６
０．５５％
Ｈ：（実測値）９．６６％
（計算値） ９．６８％
ケン化価 （実測値）１００．２（計算値）１０
１．１
動粘度 （１００℃） ２６０．４ｃＳｔ重量平均分
子量 １２０００
共重合体の赤外線吸収スペクトル図を図１に示す。Copolymer analysis value Elemental analysis C: (actual value) 60.52% (calculated value) 6
0.55% H: (actual value) 9.66% (calculated value) 9.68% Saponification value (actual value) 100.2 (calculated value) 10
1.1 Kinematic viscosity (100°C) 260.4 cSt Weight average molecular weight 12000 The infrared absorption spectrum of the copolymer is shown in FIG.
実施例２〜９
実施例１と同様の方法によシ、製造例で得た一般式（１
）のアルケニルニーテルト無水マレイン酸および他の単
量体を表２に示した組成１重合条件で重合を行なった。Examples 2 to 9 By the same method as in Example 1, the general formula (1
) and other monomers were polymerized under the composition 1 polymerization conditions shown in Table 2.
なお、溶媒を使用する場合は単量体の合計重量と同じ重
量を用いた。また。In addition, when using a solvent, the same weight as the total weight of monomers was used. Also.
重合開始剤の使用量は単量体の合計重量に対する重量％
で表わした。The amount of polymerization initiator used is % by weight based on the total weight of monomers.
It was expressed as
得られた共重合体の分析結果を表３に示す。Table 3 shows the analysis results of the obtained copolymer.
この結果から１本発明のアルケニルエーテル−無水マレ
イン酸共重合体は種々の分子量のものが存在することが
わかる。This result shows that the alkenyl ether-maleic anhydride copolymer of the present invention has various molecular weights.
表 ３Table 3
図１は実施例１の共重合体の赤外線吸収スペクトル図で
ある。
特許出願人 日本油脂株式会社FIG. 1 is an infrared absorption spectrum diagram of the copolymer of Example 1. Patent applicant: NOF Corporation
Claims (1)
マレイン酸との共重合体で、必要によりさらに他の単量
体との共重合体であり、アルケニルエーテルと無水マレ
イン酸と他の単量体とのモル比が５〜６０：４０〜７０
：０〜４０であるアルケニルエーテル−無水マレイン酸
共重合体。 ▲数式、化学式、表等があります▼・・・（１） （ただし、Ｂは２〜８個の水酸基を持つ化合物の残基、
ＡＯは炭素数２〜１８のオキシアルキレン基の１種また
は２種以上の混合物で、２種以上のときはブロック状に
付加していてもランダム状に付加していてもよく、Ｘは
炭素数２〜５のアルケニル基、Ｙはジカルボン酸または
トリカルボン酸のアシル基、または炭素数１〜３のアル
キレン基を表わし、Ｒは炭素数１〜２４の炭化水素基、
１≦ａ≦７、０≦ｂ≦６、０≦ｃ≦６、かつ１≦ａ＋ｂ
＋ｃ≦７であり、ｋ、ｌ、ｍ、ｎはオキシアルキレン基
の平均付加モル数でそれぞれ０〜１０００、かつｋ＋ａ
ｌ＋ｂｍ＋ｃｎ＝１〜３０００、ｐは１または２である
。）[Claims] 1. A copolymer of an alkenyl ether represented by the general formula (1) and maleic anhydride, which is a copolymer with other monomers if necessary, and a copolymer of an alkenyl ether and maleic anhydride. Molar ratio of acid and other monomers is 5-60:40-70
:0-40 alkenyl ether-maleic anhydride copolymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, B is the residue of a compound having 2 to 8 hydroxyl groups,
AO is one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 18 carbon atoms, and when there are two or more kinds, they may be added in a block shape or in a random shape, and X is the number of carbon atoms. 2-5 alkenyl group, Y represents an acyl group of dicarboxylic acid or tricarboxylic acid, or an alkylene group having 1-3 carbon atoms, R is a hydrocarbon group having 1-24 carbon atoms,
1≦a≦7, 0≦b≦6, 0≦c≦6, and 1≦a+b
+c≦7, k, l, m, n are the average number of added moles of oxyalkylene groups, each from 0 to 1000, and k+a
l+bm+cn=1-3000, p is 1 or 2. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125014A JP2621345B2 (en) | 1988-05-24 | 1988-05-24 | Alkenyl ether-maleic anhydride copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125014A JP2621345B2 (en) | 1988-05-24 | 1988-05-24 | Alkenyl ether-maleic anhydride copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01297411A true JPH01297411A (en) | 1989-11-30 |
| JP2621345B2 JP2621345B2 (en) | 1997-06-18 |
Family
ID=14899726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63125014A Expired - Fee Related JP2621345B2 (en) | 1988-05-24 | 1988-05-24 | Alkenyl ether-maleic anhydride copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2621345B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0490681A1 (en) | 1990-12-12 | 1992-06-17 | W.R. Grace & Co.-Conn. | Additive composition for cement admixture |
| US5362323A (en) * | 1992-02-14 | 1994-11-08 | W. R. Grace & Co. Conn. | Cement admixture composition |
| JP2008069070A (en) * | 1996-12-26 | 2008-03-27 | Nippon Shokubai Co Ltd | Cement dispersant, use thereof, and its production method |
-
1988
- 1988-05-24 JP JP63125014A patent/JP2621345B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0490681A1 (en) | 1990-12-12 | 1992-06-17 | W.R. Grace & Co.-Conn. | Additive composition for cement admixture |
| US5223036A (en) * | 1990-12-12 | 1993-06-29 | W. R. Grace & Co.-Conn. | Additive composition for cement admixture |
| US5362323A (en) * | 1992-02-14 | 1994-11-08 | W. R. Grace & Co. Conn. | Cement admixture composition |
| JP2008069070A (en) * | 1996-12-26 | 2008-03-27 | Nippon Shokubai Co Ltd | Cement dispersant, use thereof, and its production method |
| JP4538035B2 (en) * | 1996-12-26 | 2010-09-08 | 株式会社日本触媒 | Cement dispersant and cement composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2621345B2 (en) | 1997-06-18 |
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