JP2009242611A - Copolymer production method - Google Patents
Copolymer production method Download PDFInfo
- Publication number
- JP2009242611A JP2009242611A JP2008091309A JP2008091309A JP2009242611A JP 2009242611 A JP2009242611 A JP 2009242611A JP 2008091309 A JP2008091309 A JP 2008091309A JP 2008091309 A JP2008091309 A JP 2008091309A JP 2009242611 A JP2009242611 A JP 2009242611A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- compound
- carboxylic acid
- group
- unsaturated carboxylic
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000004568 cement Substances 0.000 claims abstract description 15
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims description 25
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- 238000012662 bulk polymerization Methods 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 150000002689 maleic acids Chemical class 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000001879 gelation Methods 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000000049 pigment Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910001873 dinitrogen Inorganic materials 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 125000005394 methallyl group Chemical group 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 2
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 2
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- XFJPESDYWYMVJQ-UHFFFAOYSA-N (3,3,5-trimethylcyclohexanecarbonyl) 3,3,5-trimethylcyclohexane-1-carboperoxoate Chemical compound C1C(C)(C)CC(C)CC1C(=O)OOC(=O)C1CC(C)(C)CC(C)C1 XFJPESDYWYMVJQ-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical class CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- QZYOLNVEVYIPHV-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)peroxybenzene Chemical compound CC1=CC=CC(OOC=2C=C(C)C=CC=2)=C1 QZYOLNVEVYIPHV-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-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
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VUDVPVOIALASLB-UHFFFAOYSA-N 2-[(2-cyano-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)(C#N)N=NC(C)(CO)C#N VUDVPVOIALASLB-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- IEYASXGZDIWRMO-UHFFFAOYSA-N 2-bromo-4-(2-hydroxyethoxy)-5-methoxybenzonitrile Chemical compound COC1=CC(C#N)=C(Br)C=C1OCCO IEYASXGZDIWRMO-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- 125000006026 2-methyl-1-butenyl group Chemical group 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
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000567 Amalgam (chemistry) Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ALBJGICXDBJZGK-UHFFFAOYSA-N [1-[(1-acetyloxy-1-phenylethyl)diazenyl]-1-phenylethyl] acetate Chemical compound C=1C=CC=CC=1C(C)(OC(=O)C)N=NC(C)(OC(C)=O)C1=CC=CC=C1 ALBJGICXDBJZGK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- HRYGOPGASPGRAD-UHFFFAOYSA-N carboxyoxy 1,2-dimethoxypropan-2-yl carbonate Chemical compound COCC(C)(OC)OC(=O)OOC(O)=O HRYGOPGASPGRAD-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000005332 diethylamines Chemical class 0.000 description 1
- 150000004656 dimethylamines Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- WPONNXIJPKZHGB-UHFFFAOYSA-N formaldehyde;sulfamic acid Chemical compound O=C.NS(O)(=O)=O WPONNXIJPKZHGB-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylcyclohexane Chemical compound OO.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- QHDZGOLELSOUFO-UHFFFAOYSA-N tert-butyl butaneperoxoate Chemical compound CCCC(=O)OOC(C)(C)C QHDZGOLELSOUFO-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 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
- SSBBXKVCFFZKCZ-UHFFFAOYSA-N tert-butylperoxy propyl carbonate Chemical compound CCCOC(=O)OOOC(C)(C)C SSBBXKVCFFZKCZ-UHFFFAOYSA-N 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、ポリオキシアルキレン化合物及び不飽和カルボン酸系化合物を塊状重合することを特徴とする、共重合体の製造方法に関する。 The present invention relates to a method for producing a copolymer, characterized by bulk polymerization of a polyoxyalkylene compound and an unsaturated carboxylic acid compound.
従来、ポリオキシアルキレン化合物及び不飽和カルボン酸系化合物を共重合して得られる共重合体は、セメント用添加剤や各種顔料分散剤として有用であり、幅広く使用されている。このような共重合体を製造する方法としては溶液重合、塊状重合が行われている。 Conventionally, a copolymer obtained by copolymerizing a polyoxyalkylene compound and an unsaturated carboxylic acid compound is useful as a cement additive or various pigment dispersants, and is widely used. As a method for producing such a copolymer, solution polymerization and bulk polymerization are performed.
溶液重合の溶媒として使用されるアルコール類の中には、無水マレイン酸やマレイン酸中のカルボン酸とエステル化反応を起こすものもあるため、そのうちの限られたものしか使用することができない。また、溶液重合は、溶媒を多量に使用するため、反応後に溶媒を除去する際に多大な時間を要するだけでなく、回収用の設備が必要となる。さらに、溶媒を除去する必要が無い場合でも、溶媒が共重合体中に多量に残るため、その使用用途が限定されるという問題があった。特に、水を溶媒として用いる場合、その反応系で有効な重合開始剤の殆どが無機塩であるため、溶媒の有無に関わらず、共重合体中に無機塩が残存することとなる。このような無機塩の残存した共重合体は、強熱残分の残存による悪影響が敬遠されるセラミック電子部品製造用添加剤としては使用ができない。そのため、溶液重合において水を溶媒として用いた場合には、溶媒除去の有無に関わらず、得られる共重合体の用途が限定されるという問題があった。 Some alcohols used as a solvent for solution polymerization cause esterification with maleic anhydride or carboxylic acid in maleic acid, so only a limited number of them can be used. In addition, since the solution polymerization uses a large amount of a solvent, not only does it take a long time to remove the solvent after the reaction, but also a recovery facility is required. Furthermore, even when it is not necessary to remove the solvent, a large amount of the solvent remains in the copolymer. In particular, when water is used as a solvent, most of the polymerization initiator effective in the reaction system is an inorganic salt, so that the inorganic salt remains in the copolymer regardless of the presence or absence of the solvent. Such a copolymer in which an inorganic salt remains cannot be used as an additive for producing a ceramic electronic component in which adverse effects due to the residue of the ignition residue are avoided. Therefore, when water is used as a solvent in the solution polymerization, there is a problem that the use of the obtained copolymer is limited regardless of whether or not the solvent is removed.
そこで、上記の問題を解決するために、溶液重合に代えて、溶媒を全く使用しない塊状重合が行われている。しかし、この重合方法では、原料のポリオキシアルキレン化合物中に水酸基が存在すると、その水酸基と無水マレイン酸やマレイン酸中のカルボン酸との間でエステル化反応が進行し、ゲル化を引き起こすという問題がある。また、ゲル化が起きない場合でも、当該方法により得られる共重合体を含有する分散剤は、無機粉体に添加して使用する際に所望の分散性が得られないという問題がある。 Therefore, in order to solve the above problem, bulk polymerization without using any solvent is performed instead of solution polymerization. However, in this polymerization method, when a hydroxyl group is present in the raw material polyoxyalkylene compound, the esterification reaction proceeds between the hydroxyl group and maleic anhydride or carboxylic acid in maleic acid, causing gelation. There is. Further, even when gelation does not occur, a dispersant containing a copolymer obtained by the method has a problem that desired dispersibility cannot be obtained when used by adding to an inorganic powder.
これらの問題を解決するために、原料ポリオキシアルキレン化合物中の水酸基の量を減らして塊状重合を行う方法、又は水酸基を含まないようにして塊状重合を行う方法が開示されている（例えば、特許文献１）。これらの水酸基の量を減らした、又は含まないポリオキシアルキレン化合物を製造する方法としては、過剰のアルカリと有機ハロゲン化物とを用いることが開示されている（例えば、特許文献２）。しかし、この方法は未反応物原料を除去する工程が必要であるため歩留を低下させ、また廃棄物が排出されるため環境負荷が生じるといった問題が指摘されている。 In order to solve these problems, a method of performing bulk polymerization by reducing the amount of hydroxyl groups in the raw material polyoxyalkylene compound, or a method of performing bulk polymerization without containing hydroxyl groups (for example, patents) is disclosed. Reference 1). As a method for producing a polyoxyalkylene compound in which the amount of these hydroxyl groups is reduced or not contained, use of an excess alkali and an organic halide is disclosed (for example, Patent Document 2). However, it has been pointed out that this method requires a step for removing unreacted raw materials, so that the yield is lowered, and waste is discharged, resulting in an environmental burden.
本発明は、上記の問題点に鑑み、水酸基を有するポリオキシアルキレン化合物及び不飽和カルボン酸系化合物を塊状重合してもゲル化することなく、かつ、得られた共重合体を、例えばセメント、セラミック、顔料、フィラー等の無機粉体又は有機粉体含有組成物などの粉体に添加する場合に、その粉体の分散性を高めることができる、共重合体の製造方法を提供することを目的としてなされたものである。 In view of the above problems, the present invention does not gel even when bulk polymerization is performed on a polyoxyalkylene compound having an hydroxyl group and an unsaturated carboxylic acid compound, and the obtained copolymer is used, for example, as a cement, To provide a method for producing a copolymer, which can improve the dispersibility of a powder when added to a powder such as an inorganic powder such as ceramic, pigment, filler, or an organic powder-containing composition. It was made as a purpose.
すなわち本発明は、以下のとおりである。
［１］下記一般式（１）で示されるポリオキシアルキレン化合物（ａ）と、不飽和カルボン酸系化合物（ｂ）とを、塊状重合することを特徴とする、共重合体の製造方法。
That is, the present invention is as follows.
[1] A method for producing a copolymer, comprising subjecting a polyoxyalkylene compound (a) represented by the following general formula (1) and an unsaturated carboxylic acid compound (b) to bulk polymerization.
（化１）
Ｒ１Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ（ＡＯ）ｍＨ （１）
(Chemical formula 1)
R 1 O (CH 2 CH 2 O) n (AO) m H (1)
［式中、ＡＯは炭素数３〜４のオキシアルキレン基の１種又は２種以上の付加物を示し、Ｒ１は炭素数２〜５のアルケニル基を示し、ｎは２０〜１３５を示し、ｍは１〜８を示し、（ＡＯ）ｍの化合物（ａ）全体に対する割合が１〜２５質量％である］
［２］不飽和カルボン酸系化合物（ｂ）が、マレイン酸系化合物である上記［１］記載の共重合体の製造方法。
［３］マレイン酸系化合物が、無水マレイン酸、マレイン酸及びマレイン酸エステルよりなる群から選ばれる少なくとも１種である、上記［２］記載の共重合体の製造方法。
［４］上記［１］〜［３］記載の製造方法により得られる共重合体を有効成分とする、セメント用分散剤。
[Wherein, AO represents one or more adducts of oxyalkylene groups having 3 to 4 carbon atoms, R 1 represents an alkenyl group having 2 to 5 carbon atoms, n represents 20 to 135, m represents 1 to 8, and the ratio of (AO) m to the whole compound (a) is 1 to 25% by mass]
[2] The method for producing a copolymer according to the above [1], wherein the unsaturated carboxylic acid compound (b) is a maleic acid compound.
[3] The method for producing a copolymer according to the above [2], wherein the maleic acid compound is at least one selected from the group consisting of maleic anhydride, maleic acid and maleic acid ester.
[4] A dispersant for cement containing a copolymer obtained by the production method according to the above [1] to [3] as an active ingredient.
本発明は、特定構造のポリオキシアルキレン化合物を選択した結果、原料化合物の水酸基を減らさないでも、ゲル化させることなく、不飽和カルボン酸系化合物との塊状重合を行うことを可能とした。得られた共重合体は、溶液重合によって得られる共重合体におけるような溶媒や塩の残留がないため、無機・有機粉体の分散剤として種々の用途に使用可能であり、また優れた分散性を与えることができる。 As a result of selecting a polyoxyalkylene compound having a specific structure, the present invention makes it possible to perform bulk polymerization with an unsaturated carboxylic acid compound without gelation without reducing the hydroxyl group of the raw material compound. The resulting copolymer has no residual solvent or salt as in the copolymer obtained by solution polymerization, so it can be used for various applications as a dispersant for inorganic and organic powders, and has excellent dispersion properties. Can give sex.
本発明の共重合体の製造方法は、上記一般式（１）で示されるポリオキシアルキレン化合物（ａ）を必須の原料とする。 The method for producing a copolymer of the present invention uses the polyoxyalkylene compound (a) represented by the general formula (1) as an essential raw material.
上記一般式（１）においてＲ１で示される「炭素数２〜５のアルケニル基」としては、例えば、ビニル基、イソプロペニル基、アリル基、メタリル基、３−ブテニル基、２−メチル−１−ブテニル基、３−メチル−１−ブテニル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基などが挙げられ、なかでも好ましくはアリル基、メタリル基、２−メチル−１−ブテニル基、３−メチル−１−ブテニル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基であり、より好ましくはアリル基、メタリル基である。 Examples of the “alkenyl group having 2 to 5 carbon atoms” represented by R 1 in the general formula (1) include a vinyl group, an isopropenyl group, an allyl group, a methallyl group, a 3-butenyl group, and 2-methyl-1 -Butenyl group, 3-methyl-1-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group and the like are preferable, among which allyl group, methallyl group, 2-methyl-1 are preferable. -Butenyl group, 3-methyl-1-butenyl group, 2-methyl-3-butenyl group and 3-methyl-3-butenyl group, more preferably allyl group and methallyl group.
上記一般式（１）において、ＡＯで示される「炭素数３〜４のオキシアルキレン基の１種又は２種以上の付加物」としては、例えば、オキシプロピレン基、１，２−オキシブチレン基、オキシテトラメチレン基などが挙げられ、なかでも好ましくはオキシプロピレン基、１，２−オキシブチレン基である。かかる炭素数３〜４のオキシアルキレン基は１種であっても２種以上の付加物であってもよく、２種以上の付加物である場合、その付加形式はランダム状であってもブロック状であってもよい。 In the general formula (1), examples of the “one or two or more adducts of oxyalkylene group having 3 to 4 carbon atoms” represented by AO include, for example, an oxypropylene group, a 1,2-oxybutylene group, Examples thereof include an oxytetramethylene group, and among them, an oxypropylene group and a 1,2-oxybutylene group are preferable. The oxyalkylene group having 3 to 4 carbon atoms may be one kind or two or more kinds of adducts. In the case of two or more kinds of adducts, the addition form may be random or blocked. It may be a shape.
また、（ＡＯ）ｍの、上記一般式（１）で示されるポリオキシアルキレン化合物（ａ）全体に対する割合は、１〜２５質量％の範囲内であり、より好ましくは２〜２０質量％の範囲内であり、特に２〜１５質量％の範囲内であることが好ましい。（ＡＯ）ｍの割合が上記一般式（１）で示されるポリオキシアルキレン化合物（ａ）全体の２５質量％を超えると、得られる共重合体を分散剤として用いる際において、分散性の低下を招くため好ましくない。特に、セメント用分散剤として用いると、空気連行性の増加を引き起こし、空気量を抑えるために、分散剤の添加量を減少させるか、又は別途消泡剤を添加しなければならなくなる。分散剤の添加量の減少は、分散性の低下を起こすため好ましくなく、また消泡剤の添加は、その量や種類により分散性に影響を与えるため、その選択が困難であり好ましくない。逆に、１質量％未満であると、共重合体製造時にゲル化するため好ましくない。 The ratio of (AO) m to the whole polyoxyalkylene compound (a) represented by the general formula (1) is in the range of 1 to 25% by mass, more preferably in the range of 2 to 20% by mass. It is preferable that it is in the range of 2-15 mass% especially. (AO) When the proportion of m exceeds 25% by mass of the whole polyoxyalkylene compound (a) represented by the above general formula (1), when the resulting copolymer is used as a dispersant, the dispersibility is reduced. It is not preferable because it invites. In particular, when used as a dispersant for cement, it causes an increase in air entrainment, and in order to suppress the amount of air, it is necessary to reduce the amount of the dispersant added or to separately add an antifoaming agent. A decrease in the amount of the dispersant added is not preferable because it causes a decrease in dispersibility, and the addition of an antifoaming agent is not preferable because it affects the dispersibility depending on the amount and type of the dispersant and is difficult to select. On the other hand, if it is less than 1% by mass, it is not preferable because gelation occurs during the production of the copolymer.
上記一般式（１）において、ｍは、「炭素数３〜４のオキシアルキレン基の平均付加モル数」を示し、具体的には１〜８である。なお、ｍが０である場合、すなわち一般式（１）で示されるポリオキシアルキレン化合物が（ＡＯ）を有さない場合は、重合反応においてゲル化が起こるため、所望の共重合体が得られない。
また、ｎは、「オキシエチレン基の平均付加モル数」を示し、通常２０〜１３５をであり、好ましくは２０〜１００である。
In the said General formula (1), m shows "the average added mole number of a C3-C4 oxyalkylene group", and is specifically 1-8. When m is 0, that is, when the polyoxyalkylene compound represented by the general formula (1) does not have (AO), gelation occurs in the polymerization reaction, so that a desired copolymer can be obtained. Absent.
Moreover, n shows "the average addition mole number of an oxyethylene group", and is 20-135 normally, Preferably it is 20-100.
本発明の製造方法は、上記一般式（１）で示されるポリオキシアルキレン化合物を、１種のみ用いるものであっても良く、２種以上用いるものであっても良い。 In the production method of the present invention, only one type of polyoxyalkylene compound represented by the general formula (1) may be used, or two or more types may be used.
一般式（１）で示されるポリオキシアルキレン化合物の製造方法としては、特に限定されるものではなく、例えば、アルケニルアルコールにエチレンオキシドを付加重合し、ポリオキシエチレンモノアルケニルエーテルとした後に、炭素数３〜４のアルキレンオキシドを付加重合することにより製造する方法などが挙げられる。該アルキレンオキシドを付加重合する際の触媒としては、アルカリ金属及びアルカリ土類金属やそれらの水酸化物、あるいはアルコラート等のアルカリ触媒などが用いられる。具体的には、例えば、ナトリウム、カリウム、ナトリウムカリウムアマルガム、水酸化ナトリウム、水酸化カリウム、ナトリウムハイドライド、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド等が挙げられる。 The production method of the polyoxyalkylene compound represented by the general formula (1) is not particularly limited. For example, after addition polymerization of alkenyl alcohol with ethylene oxide to form polyoxyethylene monoalkenyl ether, the number of carbon atoms is 3 The method of manufacturing by addition-polymerizing -4 alkylene oxide is mentioned. As the catalyst for addition polymerization of the alkylene oxide, alkali metals and alkaline earth metals, their hydroxides, or alkali catalysts such as alcoholates are used. Specific examples include sodium, potassium, sodium potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
これらの触媒と出発原料であるアルケニルアルコールとの混合物に、窒素ガス等の不活性ガス雰囲気下で５０〜１６０℃にてエチレンオキシド、続いて炭素数３〜４のアルキレンオキシドを付加することにより、上記一般式（１）で示されるポリオキシアルキレン化合物を得ることができる。 By adding ethylene oxide followed by alkylene oxide having 3 to 4 carbon atoms at 50 to 160 ° C. in an inert gas atmosphere such as nitrogen gas to a mixture of these catalysts and the starting material alkenyl alcohol, the above-mentioned A polyoxyalkylene compound represented by the general formula (1) can be obtained.
本発明の製造方法において必須の原料として用いられる不飽和カルボン酸系化合物（ｂ）としては、無水マレイン酸、マレイン酸、マレイン酸のアミン類の塩、マレイン酸エステル等のマレイン酸系化合物；（メタ）アクリル酸、（メタ）アクリル酸のアミン類の塩、（メタ）アクリル酸エステル等の（メタ）アクリル酸系化合物；イタコン酸、無水イタコン酸、イタコン酸のアミン類の塩、イタコン酸エステル等のイタコン酸系化合物；フマル酸、フマル酸のアミン類の塩、フマル酸エステル等のフマル酸系化合物；クロトン酸、クロトン酸のアミン類の塩、クロトン酸エステル等のクロトン酸系化合物などが挙げられ、好ましくは無水マレイン酸、マレイン酸及びマレイン酸エステルである。また、不飽和カルボン酸系化合物（ｂ）は１種単独で使用することもできるし、２種以上の混合物として使用することもできる。 Examples of the unsaturated carboxylic acid compound (b) used as an essential raw material in the production method of the present invention include maleic acid compounds such as maleic anhydride, maleic acid, salts of maleic acid amines, and maleic acid esters; (Meth) acrylic acid, (meth) acrylic acid amine salts, (meth) acrylic acid-based compounds such as (meth) acrylic acid esters; itaconic acid, itaconic anhydride, itaconic acid amine salts, itaconic acid esters Itaconic acid compounds such as fumaric acid, fumaric acid amine salts, fumaric acid esters such as fumaric acid esters, etc .; crotonic acid, crotonic acid amine salts, crotonic acid based compounds such as crotonic acid esters, etc. Preferred are maleic anhydride, maleic acid and maleic acid esters. Moreover, unsaturated carboxylic acid type compound (b) can also be used individually by 1 type, and can also be used as a 2 or more types of mixture.
上記アミン類の塩としては、例えば、アンモニウム塩、ジアンモニウム塩などのアンモニウム塩；メチルアミン塩、ジメチルアミン塩、トリメチルアミン塩、エチルアミン塩、ジエチルアミン塩、トリエチルアミン塩等のアルキルアミン塩；モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩、メチルエタノールアミン塩等のアルカノールアミン塩が挙げられる。また、上記エステルとしては、例えば、メタノール、エタノール等の飽和アルコール；ポリアルキレングリコール、ポリオキシアルキレンモノアルキルエーテル等のポリアルキレングリコール誘導体とのエステル化物が挙げられる。 Examples of the amine salts include ammonium salts such as ammonium salts and diammonium salts; alkylamine salts such as methylamine salts, dimethylamine salts, trimethylamine salts, ethylamine salts, diethylamine salts, and triethylamine salts; monoethanolamine salts. And alkanolamine salts such as diethanolamine salt, triethanolamine salt, and methylethanolamine salt. Examples of the ester include saturated alcohols such as methanol and ethanol; and esterified products with polyalkylene glycol derivatives such as polyalkylene glycol and polyoxyalkylene monoalkyl ether.
共重合体を製造する際の仕込みの割合は、式（１）で示されるポリオキシアルキレン化合物（ａ）と不飽和カルボン酸系化合物（ｂ）との和を１００％とした時、式（１）で示されるポリオキシアルキレン化合物（ａ）が通常２０〜７０モル％、好ましくは３０〜６０モル％であり、不飽和カルボン酸系化合物（ｂ）が
通常３０〜８０モル％、好ましくは４０〜７０モル％である。その他、ポリオキシアルキレン化合物（ａ）及び不飽和カルボン酸系化合物（ｂ）と共重合可能な単量体を含んでも良く、共重合可能な単量体としては、例えば、スチレン、酢酸ビニル、ビニルスルホン酸、アリルスルホン酸、メタリルスルホン酸、アクリロニトリル、メタクリロニトリル、イソブチレン、ジイソブチレン、ビニルシクロヘキサンなどのエチレン性不飽和結合を有する化合物が挙げられ、仕込みの割合は、単量体（ａ）及び（ｂ）の合計仕込量に対し２０モル％以下である。
When the copolymer is produced, the ratio of the charge is calculated by the formula (1) when the sum of the polyoxyalkylene compound (a) represented by the formula (1) and the unsaturated carboxylic acid compound (b) is 100%. ) Is usually 20 to 70 mol%, preferably 30 to 60 mol%, and the unsaturated carboxylic acid compound (b) is usually 30 to 80 mol%, preferably 40 to 40 mol%. 70 mol%. In addition, a monomer copolymerizable with the polyoxyalkylene compound (a) and the unsaturated carboxylic acid compound (b) may be included. Examples of the copolymerizable monomer include styrene, vinyl acetate, and vinyl. Examples thereof include compounds having an ethylenically unsaturated bond such as sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylonitrile, methacrylonitrile, isobutylene, diisobutylene and vinylcyclohexane. And it is 20 mol% or less with respect to the total preparation amount of (b).
本発明による共重合体の製造方法は、ポリオキシアルキレン化合物（ａ）及び不飽和カルボン酸系化合物（ｂ）を塊状重合することを特徴とするものである。なお、本発明でいう「塊状重合」とは、モノマーを溶媒に溶解又は分散させることなく、重合開始剤と共に重合させる方法をいう。その反応温度は、通常０〜１２０℃であり、好ましくは２０〜１００℃である。また、反応時間は、通常１〜５０時間であり、好ましくは２〜２５時間である。 The method for producing a copolymer according to the present invention is characterized by bulk polymerization of the polyoxyalkylene compound (a) and the unsaturated carboxylic acid compound (b). In the present invention, “bulk polymerization” refers to a method of polymerizing a monomer together with a polymerization initiator without dissolving or dispersing the monomer in a solvent. The reaction temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. Moreover, reaction time is 1 to 50 hours normally, Preferably it is 2 to 25 hours.
上記重合反応に用いる重合開始剤としては、例えば、過酸化物系開始剤、アゾ系開始剤が挙げられる。 Examples of the polymerization initiator used in the polymerization reaction include peroxide initiators and azo initiators.
過酸化物系開始剤としては、例えば、ｔｅｒｔ−ブチルハイドロペルオキシド、クメンハイドロペルオキシド、ジイソプロピルベンゼンハイドロペルオキシド、２，５−ジメチルヘキサン−２，５−ジハイドロペルオキシド、１，１，３，３−テトラメチルブチルハイドロペルオキシド、２−（４−メチルシクロヘキシル）−プロパンハイドロペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、ｔｅｒｔ−ブチルクミルペルオキシド、ジクミルペルオキシド、α，α′−ビス（ｔｅｒｔ−ブチルペルオキシ）ｐ−ジイソプロピルベンゼン、α，α′−ビス（ｔｅｒｔ−ブチルペルオキシ）ｐ−イソプロピルヘキシン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン、ｔｅｒｔ−ブチルペルオキシアセテート、ｔｅｒｔ−ブチルペルオキシラウレート、ｔｅｒｔ−ブチルペルオキシベンゾエート、ジ−ｔｅｒｔ−ブチルペルオキシフタレート、２，５−ジメチル−２，５−ジ（ベンゾイルペルオキシ）ヘキサン、ｔｅｒｔ−ブチルペルオキシプロピルカーボネート、ｔｅｒｔ−ブチルペルオキシブチレート、ｔｅｒｔ−ブチルペルオキシピバレート、ｔｅｒｔ−ブチルペルオキシネオデカノエート、クミルペルオキシネオデカノエート、ｔｅｒｔ−ブチルペルオキシ−２−エチルヘキサノエート、ｔｅｒｔ−ブチルペルオキシ−３，５，５−トリメチルシクロヘキサノエート、ｔｅｒｔ−ブチルペルオキシマレエート、クミルペルオキシオクタノエート、クミルペルオキシネオヘキサノエート、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルペルオキシ）バレエート、２，２−ビス（ｔｅｒｔ−ブチルペルオキシ）ブタン、１，１−ビス（ｔｅｒｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔｅｒｔ−ブチルペルオキシ）シクロヘキサン、２，２−ビス（ｔｅｒｔ−ブチルペルオキシ）オクタン、アセチルペルオキシド、イソブチリルペルオキシド、オクタノイルペルオキシド、デカノイルペルオキシド、ラウロイルペルオキシド、３，３，５−トリメチルシクロヘキサノイルペルオキシド、ベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ｍ−トルイルペルオキシド、ジ−イソプロピルペルオキシジカーボネート、ジ−２−エチルヘキシルペルオキシジカーボネート、ジ−ｎ−プロピルペルオキシジカーボネート、ビス（４−ｔｅｒｔ−ブチルシクロヘキシル）ペルオキシジカーボネート、ジミリスチルペルオキシジカーボネート、ジメトキシイソプロピルペルオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）ペルオキシジカーボネート、ジアリルペルオキシジカーボネート、アセチルシクロヘキシルスルフォニルペルオキシド、ｔｅｒｔ−ブチルペルオキシアリルカーボネートなどが挙げられる。 Examples of the peroxide initiator include tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide, 2- (4-methylcyclohexyl) -propane hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (tert-butylperoxy) p- Diisopropylbenzene, α, α'-bis (tert-butylperoxy) p-isopropylhexyne, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5- Di (tert-Buchi Peroxy) hexyne, tert-butylperoxyacetate, tert-butylperoxylaurate, tert-butylperoxybenzoate, di-tert-butylperoxyphthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert- Butyl peroxypropyl carbonate, tert-butyl peroxybutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butylperoxy-2-ethylhexanoate, tert- Butyl peroxy-3,5,5-trimethylcyclohexanoate, tert-butyl peroxy maleate, cumyl peroxy octanoate, cumyl peroxy neohexa Noate, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (tert-butylperoxy) butane, 1,1-bis (tert-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) octane, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3, 3,5-trimethylcyclohexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbo , Di-n-propyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydi Examples include carbonate, diallylperoxydicarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyallyl carbonate, and the like.
アゾ系開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−アルボニトリル）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、ジメチル−２，２’−アゾビス（２−メチルプロピオネ−ト）、２，２’−アゾビス［２−（ヒドロキシメチル）プロピオニトリル］、１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）などが挙げられる。 Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2-methylbutyronitrile). ), 1,1′-azobis (cyclohexane-1-albonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis [2- (hydroxymethyl) propionitrile], 1,1′-azobis (1-acetoxy-1-phenylethane) and the like can be mentioned.
重合開始剤の仕込量は、単量体（ａ）及び（ｂ）の合計仕込量に対して、通常０．１〜１０モル％、好ましくは０．５〜１０モル％である。また、必要に応じて連鎖移動剤を併用して重合を行うこともできる。 The amount of the polymerization initiator charged is usually 0.1 to 10 mol%, preferably 0.5 to 10 mol%, based on the total amount of monomers (a) and (b). Moreover, it can also superpose | polymerize by using a chain transfer agent together as needed.
本発明の製造方法により得られた共重合体は、必要に応じてカルボン酸の一部又は全部をアルカリで中和、及びアルコール系化合物でエステル化することができる。なお、無水マレイン酸を用いる場合は、無水マレイン酸単位の一部又は全部を加水分解により開環してマレイン酸単位とし、さらにマレイン酸単位の一部又は全部をアルカリで中和、及びアルコール系化合物でエステル化することができる。中和の際に用いるアルカリとしては、例えば、リチウム、ナトリウム、カリウムなどアルカリ金属の水酸化物；炭酸塩又は炭酸水素塩；マグネシウム、カルシウムなどアルカリ土類金属の水酸化物；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルエタノールアミン等のアルカノールアミン；メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミンなどのアルキルアミン；アンモニアが挙げられ、これらは１種又は２種以上を混合して用い得る。また、エステル化の際に用いるアルコールとしては、例えば、メタノール、エタノール等の飽和アルコール；アリルアルコール、メタリルアルコール等の不飽和アルコール；ポリアルキレングリコール、ポリオキシアルキレンモノアルキルエーテル、ポリオキシアルキレンモノアルケニルエーテル等のポリアルキレングリコール誘導体が挙げられ、これらは１種又は２種以上を混合して用い得る。 The copolymer obtained by the production method of the present invention can be partly or wholly neutralized with an alkali and esterified with an alcohol compound, if necessary. When maleic anhydride is used, part or all of the maleic anhydride unit is ring-opened by hydrolysis to form a maleic acid unit, and further, part or all of the maleic acid unit is neutralized with an alkali, and an alcohol system. It can be esterified with a compound. Examples of the alkali used for neutralization include hydroxides of alkali metals such as lithium, sodium, and potassium; carbonates or hydrogen carbonates; hydroxides of alkaline earth metals such as magnesium and calcium; monoethanolamine, diethanolamine , Alkanolamines such as triethanolamine and methylethanolamine; alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine; and ammonia. These may be used alone or in combination of two or more. . Examples of the alcohol used for esterification include saturated alcohols such as methanol and ethanol; unsaturated alcohols such as allyl alcohol and methallyl alcohol; polyalkylene glycol, polyoxyalkylene monoalkyl ether, and polyoxyalkylene monoalkenyl. Examples include polyalkylene glycol derivatives such as ether, and these may be used alone or in combination of two or more.
また、本発明の製造方法によって得られた共重合体は、所望の特性を発揮できるものであれば、その質量平均分子量などは特に制限されないが、共重合体の質量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下「ＧＰＣ」と呼ぶ）によるポリエチレングリコール換算で、好ましくは５，０００〜３００，０００の範囲であり、より好ましくは５，０００〜１００，０００の範囲であり、特に好ましくは７，０００〜８０，０００の範囲である。共重合体の質量平均分子量をかかる範囲とすることで、より高い分散性を発揮する共重合体が製造できる。 In addition, the copolymer obtained by the production method of the present invention is not particularly limited in mass average molecular weight as long as it can exhibit desired characteristics, but the mass average molecular weight of the copolymer is determined by gel permeation. It is preferably in the range of 5,000 to 300,000, more preferably in the range of 5,000 to 100,000, and particularly preferably 7, in terms of polyethylene glycol by chromatography (hereinafter referred to as “GPC”). The range is from 000 to 80,000. By setting the mass average molecular weight of the copolymer within such a range, a copolymer exhibiting higher dispersibility can be produced.
本発明の製造方法によって得られた分散剤の形態に特に制限はなく、例えば、共重合体を単独で用いてもよく、水溶液として用いてもよく、又はトルエンやアルコール等の有機溶剤溶液として用いてもよいが、好ましくは水溶液である。なお、上記分散剤は、その効果を損なわない範囲で、必要に応じて他の分散剤と併用することも可能である。かかる他の分散剤としては、例えば、ナフタレンスルホン酸ホルムアルデヒド縮合物の塩、メラミンスルホン酸ホルムアルデヒド縮合物の塩、リグニンスルホン酸の塩、芳香族アミノスルホン酸ホルムアルデヒド縮合物の塩、ポリカルボン酸系共重合物の塩などが挙げられる。また、上記分散剤は、その効果を損なわない範囲で、必要に応じて消泡剤などの他の添加剤と併用することができる。特にセメント用途においては、かかる他の添加剤として、空気連行剤、消泡剤、分離低減剤、凝結遅延剤、凝結促進剤、膨張剤、乾燥収縮低減剤、防錆剤などが挙げられる。 There is no restriction | limiting in particular in the form of the dispersing agent obtained by the manufacturing method of this invention, For example, a copolymer may be used independently and may be used as aqueous solution, or it uses as organic solvent solutions, such as toluene and alcohol. However, it is preferably an aqueous solution. In addition, the said dispersing agent can also be used together with another dispersing agent as needed in the range which does not impair the effect. Such other dispersants include, for example, naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde condensate salt, lignin sulfonic acid salt, aromatic amino sulfonic acid formaldehyde condensate salt, polycarboxylic acid type co-polymer, Examples thereof include a salt of a polymer. Moreover, the said dispersing agent can be used together with other additives, such as an antifoamer, in the range which does not impair the effect. Particularly in cement applications, examples of such other additives include air entraining agents, antifoaming agents, separation reducing agents, setting retarders, setting accelerators, swelling agents, drying shrinkage reducing agents, and rust inhibitors.
本発明の分散剤を使用する方法としては、特に制限はなく、例えば、粉体に予め該分散剤を添加して分散媒中に分散させる方法や、分散媒に予め該分散剤を添加した後に粉体を分散させる方法、分散媒に粉体を添加した後に該分散剤を添加し分散させる方法などが挙げられる。本発明の分散剤は、各種粉体に対して有効成分である共重合体を０．０１〜５０質量％、好ましくは０．１〜３０質量％添加して使用することができる。 The method of using the dispersant of the present invention is not particularly limited, for example, a method of adding the dispersant to the powder in advance and dispersing it in the dispersion medium, or after adding the dispersant to the dispersion medium in advance. Examples thereof include a method of dispersing the powder and a method of adding and dispersing the dispersant after adding the powder to the dispersion medium. The dispersant of the present invention can be used by adding 0.01 to 50% by mass, preferably 0.1 to 30% by mass of a copolymer which is an active ingredient to various powders.
さらに、上記分散剤は、各種の有機・無機粉体に適用し得、セメント用途、セラミック用途、塗料用途、樹脂用途などに用いることができる。なかでも、セメント用途が好ましく、本発明の分散剤を用いることで優れた分散性を与えることができる。 Furthermore, the dispersant can be applied to various organic and inorganic powders, and can be used for cement, ceramics, paints, resins, and the like. Of these, cement is preferred, and excellent dispersibility can be imparted by using the dispersant of the present invention.
以下に、実施例を挙げて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
＜実施例１＞
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイル及び蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、アリルアルコール５８ｇ（１．０モル）及びナトリウムメトキシド１．０ｇを仕込み、系内を窒素ガスで置換した。攪拌下、１００〜１２０℃、０．０５〜０．５ＭＰａ（ゲージ圧）の条件で、別に用意した耐圧容器よりエチレンオキシド２７７５ｇ（６３モル）を窒素ガス圧により加圧添加した。添加終了後、同条件で内圧が一定となるまで反応させ、窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰａ（ゲージ圧）以下で０．５時間処理を行なった後、窒素ガスで０．０５ＭＰａ（ゲージ圧）まで加圧した。加圧後、１００〜１２０℃、０．０５〜０．５ＭＰａ（ゲージ圧）の条件で、別に用意した耐圧容器よりプロピレンオキシド５８ｇ（１．０モル）を窒素ガス圧により加圧添加した。同条件で内圧が一定となるまで反応させた後、窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰａ（ゲージ圧）以下で０．５時間処理を行なった後、窒素ガスで０．０５ＭＰａ（ゲージ圧）まで加圧し、反応物２３１３ｇ（０．８０モル）を３Ｌナスフラスコに抜き取った。その後、塩酸で中和し水や副生した塩を除いて目的とするポリオキシアルキレン化合物を得た。その後、かき混ぜ機、温度計、窒素ガス導入管を装着した３Ｌ四つ口フラスコに、ポリオキシアルキレン化合物１，４４６ｇ（０．５０モル）と無水マレイン酸６９ｇ（０．７０モル）を秤り取り、重合開始剤としてベンゾイルペルオキシド７ｇ（０．０３モル）を添加し、窒素ガス雰囲気下、８０±２℃で１０時間反応させることにより、目的とする共重合体を得た。
<Example 1>
A stainless steel 5 L high-pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blowing pipe, exhaust pipe, cooling coil and steam jacket was added 58 g (1.0 mol) of allyl alcohol and sodium methoxide 1 0.0 g was charged and the inside of the system was replaced with nitrogen gas. Under stirring, under conditions of 100 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure), 2775 g (63 mol) of ethylene oxide was added under pressure by nitrogen gas pressure from a pressure vessel prepared separately. After completion of the addition, the reaction was continued under the same conditions until the internal pressure became constant, and the treatment was performed at 70 to 80 ° C. under 13 kPa (gauge pressure) for 0.5 hours while blowing nitrogen gas, and then 0.05 MPa with nitrogen gas. Pressurized to (gauge pressure). After pressurization, 58 g (1.0 mol) of propylene oxide was added under pressure by nitrogen gas pressure from a pressure vessel prepared separately under the conditions of 100 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). After reacting until the internal pressure becomes constant under the same conditions, treatment was performed at 70 to 80 ° C. under 13 kPa (gauge pressure) for 0.5 hours while blowing nitrogen gas, and then 0.05 MPa (gauge) with nitrogen gas. Pressure) and 2313 g (0.80 mol) of the reaction product was withdrawn into a 3 L eggplant flask. Then, the target polyoxyalkylene compound was obtained by neutralizing with hydrochloric acid and removing water and by-produced salts. Then, 1,446 g (0.50 mol) of polyoxyalkylene compound and 69 g (0.70 mol) of maleic anhydride were weighed into a 3 L four-necked flask equipped with a stirrer, thermometer and nitrogen gas inlet tube. Then, 7 g (0.03 mol) of benzoyl peroxide was added as a polymerization initiator and reacted at 80 ± 2 ° C. for 10 hours in a nitrogen gas atmosphere to obtain the desired copolymer.
＜実施例２〜６＞
上記一般式（１）で示されるポリオキシアルキレン化合物、不飽和カルボン酸系化合物及びそのモル比を、下記表１のとおりにそれぞれ変更した以外は実施例１と同様に反応を行い、目的とする共重合体を得た。
<Examples 2 to 6>
The reaction is carried out in the same manner as in Example 1 except that the polyoxyalkylene compound represented by the general formula (1), the unsaturated carboxylic acid compound, and the molar ratio thereof are changed as shown in Table 1 below. A copolymer was obtained.
＜実施例７＞
実施例１と同様に反応を行い、上記一般式（１）で示されるポリオキシアルキレン化合物として、下記表１のとおりのポリオキシアルキレン化合物を得た。
その後、かき混ぜ機、温度計、窒素ガス導入管を装着した３Ｌ四つ口フラスコに、表１に示したポリオキシアルキレン化合物７７０ｇ（０．５０モル）と無水マレイン酸７４ｇ（０．７５モル）、ドデカンチオール６ｇ（０．０３モル）を秤り取り、重合開始剤として２，２’−アゾビスイソブチロニトリル８ｇ（０．０５モル）を添加し、窒素ガス雰囲気下、８０±２℃で１０時間反応させることにより、目的とする共重合体を得た。
<Example 7>
Reaction was performed in the same manner as in Example 1 to obtain polyoxyalkylene compounds as shown in Table 1 below as the polyoxyalkylene compounds represented by the general formula (1).
Thereafter, in a 3 L four-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 770 g (0.50 mol) of the polyoxyalkylene compound shown in Table 1 and 74 g (0.75 mol) of maleic anhydride, Weigh 6 g (0.03 mol) of dodecanethiol, add 8 g (0.05 mol) of 2,2′-azobisisobutyronitrile as a polymerization initiator, and at 80 ± 2 ° C. in a nitrogen gas atmosphere. The target copolymer was obtained by reacting for 10 hours.
＜比較例１〜３＞
上記一般式（１）で示されるポリオキシアルキレン化合物、不飽和カルボン酸系化合物及びそのモル比を、下記表１のとおりにそれぞれ変更した以外は実施例１と同様に反応を行ったが、目的とする共重合体を得られず、合成中にゲル化した。
<Comparative Examples 1-3>
The reaction was carried out in the same manner as in Example 1 except that the polyoxyalkylene compound represented by the general formula (1), the unsaturated carboxylic acid compound, and the molar ratio thereof were changed as shown in Table 1 below. The copolymer was not obtained, and gelled during synthesis.
なお、上記比較例１において用いたポリオキシアルキレン化合物は下記のとおりにして得た。
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイル及び蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、アリルアルコール５８ｇ（１．０モル）及びナトリウムメトキシド１．０ｇを仕込み、系内を窒素ガスで置換した。攪拌下、１００〜１２０℃、０．０５〜０．５ＭＰａ（ゲージ圧）の条件で、別に用意した耐圧容器よりエチレンオキシド２７７５ｇ（６３モル）を窒素ガス圧により加圧添加した。添加終了後、同条件で内圧が一定となるまで反応させ、窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰａ（ゲージ圧）以下で０．５時間処理を行なった後、窒素ガスで０．０５ＭＰａ（ゲージ圧）まで加圧し、反応物２２６６ｇ（０．８０モル）を３Ｌナスフラスコに抜き取った。その後、塩酸で中和し副生した塩を除いて目的とするポリオキシアルキレン化合物を得た。
The polyoxyalkylene compound used in Comparative Example 1 was obtained as follows.
A stainless steel 5 L high-pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blowing pipe, exhaust pipe, cooling coil and steam jacket was added 58 g (1.0 mol) of allyl alcohol and sodium methoxide 1 0.0 g was charged and the inside of the system was replaced with nitrogen gas. Under stirring, under conditions of 100 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure), 2775 g (63 mol) of ethylene oxide was added under pressure by nitrogen gas pressure from a pressure vessel prepared separately. After completion of the addition, the reaction was continued under the same conditions until the internal pressure became constant, and the treatment was performed at 70 to 80 ° C. under 13 kPa (gauge pressure) for 0.5 hours while blowing nitrogen gas, and then 0.05 MPa with nitrogen gas. The pressure was increased to (gauge pressure), and 2266 g (0.80 mol) of the reaction product was extracted into a 3 L eggplant flask. Thereafter, the desired polyoxyalkylene compound was obtained by neutralizing with hydrochloric acid and removing the by-product salt.
また、上記比較例３において用いたポリオキシアルキレン化合物は下記のとおりにして得た。
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイル及び蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、アリルアルコール５８ｇ（１．０モル）及びナトリウムメトキシド１．０ｇを仕込み、系内を窒素ガスで置換した。攪拌下、１００〜１２０℃、０．０５〜０．５ＭＰａ（ゲージ圧）の条件で、別に用意した耐圧容器よりエチレンオキシド２７７５ｇ（６３モル）とプロピレンオキシド１７４ｇ（３．０モル）を混合した溶液を窒素ガス圧により加圧添加した。添加終了後、同条件で内圧が一定となるまで反応させ、窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰａ（ゲージ圧）以下で０．５時間処理を行なった後、窒素ガスで０．０５ＭＰａ（ゲージ圧）まで加圧し、反応物２４０６ｇ（０．８０モル）を３Ｌナスフラスコに抜き取った。その後、塩酸で中和し水や副生した塩を除いて目的とするポリオキシアルキレン化合物を得た。
The polyoxyalkylene compound used in Comparative Example 3 was obtained as follows.
A stainless steel 5 L high-pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blowing pipe, exhaust pipe, cooling coil and steam jacket was added 58 g (1.0 mol) of allyl alcohol and sodium methoxide 1 0.0 g was charged and the inside of the system was replaced with nitrogen gas. Under stirring, a solution prepared by mixing 2775 g (63 mol) of ethylene oxide and 174 g (3.0 mol) of propylene oxide from a pressure vessel prepared separately at 100 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). The pressure was added by nitrogen gas pressure. After completion of the addition, the reaction was continued under the same conditions until the internal pressure became constant, and the treatment was performed at 70 to 80 ° C. under 13 kPa (gauge pressure) for 0.5 hours while blowing nitrogen gas, and then 0.05 MPa with nitrogen gas. The pressure was increased to (gauge pressure), and 2406 g (0.80 mol) of the reaction product was extracted into a 3 L eggplant flask. Then, the target polyoxyalkylene compound was obtained by neutralizing with hydrochloric acid and removing water and by-produced salts.
＜比較例４、５＞
上記一般式（１）で示されるポリオキシアルキレン化合物、不飽和カルボン酸系化合物及びそのモル比を、下記表１のとおりにそれぞれ変更した以外は実施例１と同様に反応を行い、目的とする共重合体を得た。
<Comparative Examples 4 and 5>
The reaction is carried out in the same manner as in Example 1 except that the polyoxyalkylene compound represented by the general formula (1), the unsaturated carboxylic acid compound, and the molar ratio thereof are changed as shown in Table 1 below. A copolymer was obtained.
＜実施例８〜１４、比較例６及び７＞
実施例１〜７、比較例４及び５で得られた各共重合体を、それぞれイオン交換水で希釈して、２０質量％水溶液に調整し、さらに消泡剤（ポリアルキレングリコール誘導体；ディスホームＣＣ−１１８ 日油（株）製）を添加して、セメント用添加剤の形態とした。
次に、ＪＩＳＲ５２０１記載のモルタルミキサにセメント（普通ポルトランドセメント）６００ｇ、細骨材（君津産山砂）１，０２４ｇを秤り取り、低速回転で３０秒間空練りを行った。その後、直後のモルタルフローが２２０±１０ｍｍになるよう下記表２に示す割合で前記の各セメント用添加剤を添加した水道水２０７ｇを加えて低速回転で３０秒間練り混ぜ、さらに高速回転で２分間練り混ぜた後、５分間静置してモルタル組成物を調整した。なお、練り上がり直後の空気量は３．０±１．０％となるように消泡剤を添加することで調整し、温度は２３±２℃であることを確認した。
得られたモルタル組成物について、直後（５分間静置後）、３０分後（直後から３０分後）のモルタルフロー試験を行った。結果を下記表２に示す。
なお、かかるモルタルフロー試験は、１５秒間に１５回の落下運動は与えなかった以外はＪＩＳＲ５２０１に準拠して行った。また、下記表２において「セメント用添加剤の添加量」の値は、セメント用添加剤のセメントに対する質量％を示す。
<Examples 8 to 14, Comparative Examples 6 and 7>
The copolymers obtained in Examples 1 to 7 and Comparative Examples 4 and 5 were each diluted with ion-exchanged water to prepare a 20% by mass aqueous solution, and an antifoaming agent (polyalkylene glycol derivative; CC-118 NOF Co., Ltd.) was added to form a cement additive.
Next, 600 g of cement (ordinary Portland cement) and 1,024 g of fine aggregate (Kimitsu mountain sand) were weighed into a mortar mixer described in JIS R5201, and kneaded for 30 seconds at a low speed. Thereafter, 207 g of tap water added with the above-mentioned cement additives was added at a rate shown in Table 2 below so that the mortar flow immediately after was 220 ± 10 mm, and kneaded at low speed for 30 seconds, and further at high speed for 2 minutes. After kneading, the mixture was allowed to stand for 5 minutes to prepare a mortar composition. The amount of air immediately after kneading was adjusted by adding an antifoaming agent so as to be 3.0 ± 1.0%, and it was confirmed that the temperature was 23 ± 2 ° C.
The obtained mortar composition was subjected to a mortar flow test immediately after (after standing for 5 minutes) and after 30 minutes (from immediately after 30 minutes). The results are shown in Table 2 below.
In addition, this mortar flow test was performed based on JISR5201 except not giving 15 fall movements in 15 seconds. In Table 2 below, the value of “addition amount of cement additive” indicates mass% of the cement additive with respect to the cement.
表１から明らかなように、上記一般式（１）に示される構造を有しないオキシアルキレン化合物を用いた比較例１〜３の共重合体は、製造中にゲル化した。これに対し、本発明の製造方法を用いた実施例１〜７の共重合体はゲル化することなく製造することができた。
また、比較例４及び５の共重合体は、ゲル化することなく製造することができたが、これらを用いた比較例６及び７の分散剤は、実施例８〜１４の分散剤と比較すると、同程度の分散性を得るために必要とされる分散剤の添加量が多く、また、３０分後のフロー値が小さかった（表２）。したがって、実施例により得られた共重合体は、比較例により得られた共重合体に比べ、優れた分散性能や分散安定性を示していることが分かった。
As is clear from Table 1, the copolymers of Comparative Examples 1 to 3 using an oxyalkylene compound having no structure represented by the general formula (1) gelled during production. On the other hand, the copolymers of Examples 1 to 7 using the production method of the present invention could be produced without gelation.
Moreover, although the copolymer of Comparative Examples 4 and 5 was able to be manufactured without gelling, the dispersants of Comparative Examples 6 and 7 using these were compared with the dispersants of Examples 8-14. Then, the addition amount of the dispersant required for obtaining the same degree of dispersibility was large, and the flow value after 30 minutes was small (Table 2). Therefore, it was found that the copolymers obtained by Examples showed superior dispersion performance and dispersion stability compared to the copolymers obtained by Comparative Examples.
Claims (4)
（化１）
Ｒ１Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ（ＡＯ）ｍＨ （１）
［式中、ＡＯは炭素数３〜４のオキシアルキレン基の１種又は２種以上の付加物を示し、Ｒ１は炭素数２〜５のアルケニル基を示し、ｎは２０〜１３５を示し、ｍは１〜８を示し、（ＡＯ）ｍの化合物（ａ）全体に対する割合が１〜２５質量％である］ A method for producing a copolymer, comprising subjecting a polyoxyalkylene compound (a) represented by the following general formula (1) and an unsaturated carboxylic acid compound (b) to bulk polymerization.
(Chemical formula 1)
R 1 O (CH 2 CH 2 O) n (AO) m H (1)
[Wherein, AO represents one or more adducts of oxyalkylene groups having 3 to 4 carbon atoms, R 1 represents an alkenyl group having 2 to 5 carbon atoms, n represents 20 to 135, m represents 1 to 8, and the ratio of (AO) m to the whole compound (a) is 1 to 25% by mass]
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516521A (en) * | 2011-11-03 | 2012-06-27 | 武汉凯森化学有限公司 | Phenyl allyl alcohol polyether and preparation method thereof |
| US11214657B2 (en) * | 2018-09-17 | 2022-01-04 | Jiahua Science & Technology Development (Shanghai) Ltd. | Preparation method of powdery polycarboxylate superplasticizer |
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| CN102516521B (en) * | 2011-11-03 | 2013-02-27 | 武汉凯森化学有限公司 | Phenyl allyl alcohol polyether and preparation method thereof |
| US11214657B2 (en) * | 2018-09-17 | 2022-01-04 | Jiahua Science & Technology Development (Shanghai) Ltd. | Preparation method of powdery polycarboxylate superplasticizer |
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| JP5151620B2 (en) | 2013-02-27 |
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