JP6388329B2 - Water-soluble polymer dispersion containing low inorganic salt and process for producing the same - Google Patents
Water-soluble polymer dispersion containing low inorganic salt and process for producing the same Download PDFInfo
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- JP6388329B2 JP6388329B2 JP2014123003A JP2014123003A JP6388329B2 JP 6388329 B2 JP6388329 B2 JP 6388329B2 JP 2014123003 A JP2014123003 A JP 2014123003A JP 2014123003 A JP2014123003 A JP 2014123003A JP 6388329 B2 JP6388329 B2 JP 6388329B2
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- Prior art keywords
- water
- soluble polymer
- dispersion
- mass
- chloride
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- 229920003169 water-soluble polymer Polymers 0.000 title claims description 54
- 239000004815 dispersion polymer Substances 0.000 title claims description 44
- 229910017053 inorganic salt Inorganic materials 0.000 title claims description 18
- 238000000034 method Methods 0.000 title description 10
- 230000008569 process Effects 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000002270 dispersing agent Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000012674 dispersion polymerization Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 239000006185 dispersion Substances 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 11
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 9
- 235000011130 ammonium sulphate Nutrition 0.000 description 9
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 dimethyl chloride Chemical compound 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 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
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-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
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- FVPMLCUKLBYBSV-UHFFFAOYSA-M 2-hydroxypropyl-dimethyl-(prop-2-enoyloxymethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)COC(=O)C=C FVPMLCUKLBYBSV-UHFFFAOYSA-M 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GIKAVDMFTIROPO-UHFFFAOYSA-M [Cl-].C(C=C)(=O)OC[N+](C)(CC1=CC=CC=C1)CC(C)O Chemical compound [Cl-].C(C=C)(=O)OC[N+](C)(CC1=CC=CC=C1)CC(C)O GIKAVDMFTIROPO-UHFFFAOYSA-M 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QBZPCMKUFMJWAN-UHFFFAOYSA-N benzyl-dimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)NCCC[N+](C)(C)CC1=CC=CC=C1 QBZPCMKUFMJWAN-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、塩水溶液中、高分子分散剤共存下、分散重合法による無機塩含有量を抑制した水溶性重合体分散液、及びその製造方法に関するものである。 The present invention relates to a water-soluble polymer dispersion in which an inorganic salt content is suppressed by a dispersion polymerization method in a salt aqueous solution in the presence of a polymer dispersant, and a method for producing the same.
塩水溶液中でイオン性高分子分散剤を共存させ、イオン性水溶性高分子からなる分散液の技術については、種々の特許公報により開示されている。例えば、特許文献1は、単量体が塩水溶液に可溶で重合した高分子が不溶である分散液を製造するに際し、塩水溶液中に可溶なカチオン性高分子を分散剤として共存させる方法を開示している。又、特許文献2は、アニオン性又はカチオン性水溶性高分子からなる分散液を製造する場合、エチレングリコール、プロピレングリコール、グリセリンあるいはポリエチレングリコ−ルのような多価アルコールを共存させる方法である。更に特許文献3では、アニオン性又はカチオン性水溶性高分子からなる分散液を製造する場合、共存させるイオン性高分子分散剤が塩水溶液中に可溶なアニオン性あるいはカチオン性高分子からなることを開示している。又、分散重合時の増粘抑制剤として添加剤を使用する方法も種々開示されている(特許文献4、5)。これらで使用する塩水溶液を構成する塩の濃度は、何れも少なくとも15質量%必要であると記載されている。しかし、これら塩類は有効成分として作用せず、又、高分子の機能を阻害する場合があるためより少ないことが要望されている。一般的に分散重合時において無機塩として硫酸アンモニウムが汎用されているが、これらで使用するイオン性水溶性高分子からなる分散液を構成する硫酸アンモニウム塩由来の全窒素含有量は、50000ppm(対水溶性重合体分散液製品)程度は含まれている。全窒素含有量は、農作物に対して大きな影響力をもつ。植物はアンモニウム態窒素又は硝酸態窒素の形で窒素を吸収してその生育に利用する。しかし、窒素過多になるとかえって悪影響を与えることが知られており、含有量の低減が求められている。又、平成26年の水質汚濁防止法改正に伴いアンモニウム化合物が有害物質に指定されていることから硫酸アンモニウムを低減あるいは削減することができる分散重合液が要望されている。 Various patent publications disclose a technique of a dispersion liquid composed of an ionic water-soluble polymer in the presence of an ionic polymer dispersant in an aqueous salt solution. For example, Patent Document 1 discloses a method in which a cationic polymer soluble in an aqueous salt solution coexists as a dispersant when producing a dispersion in which the monomer is soluble in the aqueous salt solution and the polymerized polymer is insoluble. Is disclosed. Further, Patent Document 2 is a method in which a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin or polyethylene glycol is allowed to coexist when a dispersion comprising an anionic or cationic water-soluble polymer is produced. Furthermore, in Patent Document 3, when producing a dispersion composed of an anionic or cationic water-soluble polymer, the coexisting ionic polymer dispersant is composed of an anionic or cationic polymer that is soluble in an aqueous salt solution. Is disclosed. Various methods of using an additive as a thickening inhibitor during dispersion polymerization have also been disclosed (Patent Documents 4 and 5). It is described that the concentration of the salt constituting the salt aqueous solution used in these is at least 15% by mass. However, since these salts do not act as active ingredients and may inhibit the function of the polymer, there is a demand for less. In general, ammonium sulfate is widely used as an inorganic salt at the time of dispersion polymerization, but the total nitrogen content derived from the ammonium sulfate salt constituting the dispersion composed of the ionic water-soluble polymer used in these is 50,000 ppm (water-soluble) Polymer dispersion product) grade is included. Total nitrogen content has a great influence on crops. Plants absorb nitrogen in the form of ammonium nitrogen or nitrate nitrogen and use it for its growth. However, it is known that excessive nitrogen is adversely affected, and a reduction in the content is required. In addition, with the amendment of the Water Pollution Control Act of 2014, ammonium compounds have been designated as hazardous substances, and therefore there is a need for a dispersion polymerization solution that can reduce or reduce ammonium sulfate.
本発明は、塩水溶液中、高分子分散剤共存下、分散重合法による無機塩含有量を抑制した水溶性重合体分散液、及びその製造方法を提供することを課題とする。 An object of the present invention is to provide a water-soluble polymer dispersion in which an inorganic salt content is suppressed by a dispersion polymerization method in a salt aqueous solution in the presence of a polymer dispersant, and a method for producing the same.
上記課題を解決するため鋭意検討を行なった結果、塩化物イオン及び多価アニオンを含有する塩水溶液中、特定の単量体を必須として含有する単量体あるいは単量体混合物を、特定の高分子分散剤共存下、分散重合することで無機塩含有量を抑制した水溶性重合体分散液を得ることができる。 As a result of intensive studies to solve the above problems, a monomer or monomer mixture containing a specific monomer as an essential component in a salt aqueous solution containing chloride ions and polyvalent anions is By carrying out dispersion polymerization in the presence of a molecular dispersant, it is possible to obtain a water-soluble polymer dispersion in which the inorganic salt content is suppressed.
本発明における水溶性重合体分散液は、無機塩含有量を抑制した水溶性重合体分散液及びその製造方法であり、高分子の機能を最大限に発揮することができ、環境に放出される塩由来の窒素分の抑制を達成することができる。 The water-soluble polymer dispersion in the present invention is a water-soluble polymer dispersion having a reduced inorganic salt content and a method for producing the same, and can exhibit the function of the polymer to the maximum and is released to the environment. Inhibition of salt-derived nitrogen content can be achieved.
本発明における水溶性重合体分散液は、塩水溶液中で、下記一般式(1)で表される単量体を必須として含有する単量体あるいは単量体混合物水溶液を、該塩水溶液中に可溶な高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液である。
一般式(1)
R1は水素又はメチル基、R2、R3は炭素数1〜3のアルキル基、アルコキシ基、R4は炭素数7〜20のアルキル基あるいはアリール基である。Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基、X1は陰イオンをそれぞれ表わす。
The water-soluble polymer dispersion in the present invention contains a monomer or a monomer mixture aqueous solution containing a monomer represented by the following general formula (1) as an essential component in a salt aqueous solution. This is a water-soluble polymer dispersion obtained by coexisting a soluble polymer dispersant and dispersing polymerization with stirring.
General formula (1)
R 1 is hydrogen or a methyl group, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R 4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
本発明における水溶性重合体分散液を製造する際に使用する一般式(1)で表されるカチオン性単量体は、ジメチルアミノエチル(メタ)アクリレートあるいはジメチルアミノプロピルアクリルアミドの塩化ベンジル等のハロゲン化アリール化合物や炭素数が7〜20のハロゲン化アルキルによる4級化物等が挙げられ、これらのカチオン性ビニル系単量体は1種を単独で用いることができ、2種以上を組み合わせて用いることもできる。具体的な例としては、(メタ)アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、(メタ)アクリロイルオキシ−2−ヒドロキシプロピルベンジルジメチルアンモニウム塩化物、(メタ)アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物等である。一般式(1)で表されるカチオン性単量体は5〜100モル%の範囲が好ましく、10〜100モル%が更に好ましい。 The cationic monomer represented by the general formula (1) used for producing the water-soluble polymer dispersion in the present invention is a halogen such as dimethyl chloride of dimethylaminoethyl (meth) acrylate or dimethylaminopropylacrylamide. Cationized aryl compounds and quaternized products of alkyl halides having 7 to 20 carbon atoms. These cationic vinyl monomers can be used alone or in combination of two or more. You can also. Specific examples include (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy-2-hydroxypropylbenzyldimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, and the like. The cationic monomer represented by the general formula (1) is preferably in the range of 5 to 100 mol%, more preferably 10 to 100 mol%.
本発明における水溶性重合体分散液を製造する際に使用する一般式(1)で表されるカチオン性単量体と下記一般式(2)で表されるカチオン性単量体を共重合して使用することができる。
一般式(2)
R5は水素又はメチル基、R6、R7は炭素数1〜3のアルキルあるいはヒドロキシアルキル基、R8は水素、炭素数1〜3のアルキル基であり、Aは酸素またはNH、Bは炭素数2〜4のアルキレン基を表わす、X2 −は陰イオンをそれぞれ表わす。
A cationic monomer represented by the general formula (1) and a cationic monomer represented by the following general formula (2) used for producing the water-soluble polymer dispersion in the present invention are copolymerized. Can be used.
General formula (2)
R 5 is hydrogen or a methyl group, R 6 and R 7 are alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms, R 8 is hydrogen and an alkyl group having 1 to 3 carbon atoms, A is oxygen or NH, B is represents an alkylene group having 2 to 4 carbon atoms, X 2 - represents respectively an anion.
一般式(2)で表されるカチオン性単量体として、ジメチルアミノエチル(メタ)アクリレート等、塩化メチル等のハロゲン化アルキル等が挙げられ、これらのカチオン性単量体は1種を単独で用いることができ、2種以上を組み合わせて用いることもできる。具体的な例としては、ジメチルアミノエチル(メタ)アクリレートあるいはジメチルアミノプロピルアクリルアミドの塩化メチルや塩化エチルなど低級アルキル基のハロゲン化物による四級化物である。例えば(メタ)アクリロイルオキシエチルトリメチルアンモニウム塩化物、(メタ)アクリロイルオキシ−2−ヒドロキシプロピルトリメチルアンモニウム塩化物、(メタ)アクリロイルアミノプロピルトリメチルアンモニウム塩化物等である。 Examples of the cationic monomer represented by the general formula (2) include dimethylaminoethyl (meth) acrylate, alkyl halides such as methyl chloride, and the like. It can also be used and it can also be used in combination of 2 or more types. Specific examples include quaternized products of dimethylaminoethyl (meth) acrylate or dimethylaminopropylacrylamide with a halide of a lower alkyl group such as methyl chloride or ethyl chloride. For example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, and the like.
一般式(1)で表されるカチオン性単量体と非イオン性単量体を共重合させる場合に使用する非イオン性単量体としては、(メタ)アクリルアミド、N,N−ジメチルアクリルアミド、アクリロニトリル、(メタ)アクリル酸−2−ヒドロキシエチル、ジアセトンアクリルアミド、N−ビニルピロリドン、N−ビニルホルムアミド、N−ビニルアセトアミド、アクリロイルモルホリン等が挙げられる。これらを二種以上組み合わせて使用しても良い。又、一般式(1)で表されるカチオン性単量体と一般式(2)で表されるカチオン性単量体と非イオン性単量体を共重合させても良い。 Examples of the nonionic monomer used when the cationic monomer represented by the general formula (1) and the nonionic monomer are copolymerized include (meth) acrylamide, N, N-dimethylacrylamide, Examples include acrylonitrile, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acryloylmorpholine, and the like. Two or more of these may be used in combination. Moreover, you may copolymerize the cationic monomer represented by General formula (1), the cationic monomer represented by General formula (2), and a nonionic monomer.
本発明における水溶性重合体分散液は、イオン性が両性であっても良く、その場合は製造時に、下記一般式(3)で表されるアニオン性単量体が使用される。
一般式(3)
R9は水素、メチル基又はカルボキシメチル基、QはSO3、C6H4SO3、CONHC(CH3)2CH2SO3、C6H4COOあるいはCOO、R10は水素又はCOOY2、Y1あるいはY2は水素又は陽イオンをそれぞれ表わす。
The water-soluble polymer dispersion in the present invention may be amphoteric in ionicity. In that case, an anionic monomer represented by the following general formula (3) is used at the time of production.
General formula (3)
R 9 is hydrogen, methyl group or carboxymethyl group, Q is SO 3 , C 6 H 4 SO 3 , CONHC (CH 3 ) 2 CH 2 SO 3 , C 6 H 4 COO or COO, R 10 is hydrogen or COOY 2 , Y 1 or Y 2 each represents hydrogen or a cation.
本発明における両性水溶性重合体分散液を製造する際に使用する前記一般式(3)で表されるアニオン性単量体は0〜40モル%の範囲である。アニオン性単量体の例としては、ビニルスルホン酸、ビニルベンゼンスルホン酸あるいは2−アクリルアミド−2−メチルプロパンスルホン酸、メタクリル酸、アクリル酸、イタコン酸、マレイン酸、フタル酸あるいはp−カルボキシスチレン酸等が挙げられる。これらを二種以上組み合わせて使用しても良い。又、一般式(3)で表されるアニオン性単量体と非イオン性単量体を使用しても良く、一般式(3)で表されるアニオン性単量体と一般式(2)で表されるカチオン性単量体と非イオン性単量体を使用しても良い。 The anionic monomer represented by the general formula (3) used when producing the amphoteric water-soluble polymer dispersion in the present invention is in the range of 0 to 40 mol%. Examples of anionic monomers include vinyl sulfonic acid, vinyl benzene sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid, phthalic acid or p-carboxystyrene acid Etc. Two or more of these may be used in combination. An anionic monomer and a nonionic monomer represented by the general formula (3) may be used, and an anionic monomer represented by the general formula (3) and the general formula (2) A cationic monomer and a nonionic monomer represented by
本発明における塩水中分散重合は、特開昭62−15251号公報、特開昭62−20511号公報、あるいは特開2007−16086号公報などで開示されている常法により製造することができる。塩水溶液中において、該塩水溶液中に構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を共存させ、一般式(1)で表される単量体を必須として含有する単量体あるいは単量体混合物水溶液を分散重合する。一般式(1)で表される単量体を必須として含有して得られた水溶性重合体は、一般式(1)中のベンジル基等の疎水性基の存在により塩水溶液に溶解し難くなっており分散重合する際に適している。分散重合する際に、重合遅延性物質を全単量体に対し0.5〜5モル%添加することにより、増粘の抑制効果があり、適宜に添加して製造することができる。重合遅延性物質としては、イタコン酸、マレイン酸、フタル酸等が挙げられる。 The salt water dispersion polymerization in the present invention can be produced by a conventional method disclosed in JP-A-62-215251, JP-A-62-25111, or JP-A-2007-16086. In the salt aqueous solution, a polymer dispersant containing diallyldimethylammonium chloride as a structural unit is coexisted in the salt aqueous solution, and a monomer containing the monomer represented by the general formula (1) as an essential component or The aqueous monomer mixture solution is subjected to dispersion polymerization. The water-soluble polymer obtained by containing the monomer represented by the general formula (1) as an essential component is difficult to dissolve in an aqueous salt solution due to the presence of a hydrophobic group such as a benzyl group in the general formula (1). It is suitable for dispersion polymerization. At the time of dispersion polymerization, by adding 0.5 to 5 mol% of a polymerization retarding substance with respect to all monomers, there is an effect of suppressing thickening, and it can be produced by appropriately adding. Examples of the polymerization retarding substance include itaconic acid, maleic acid, and phthalic acid.
塩水中分散重合に使用する高分子分散剤は、本発明においては、構成単位としてジアリルジメチルアンモニウム塩化物を含有するものを使用する。ポリジアリルジメチルアンモニウム塩化物でも良いが、ジアリルジメチルアンモニウム塩化物と非イオン性単量体との共重合体も使用可能である。非イオン性単量体の例としては、アクリルアミド、N−ビニルホルムアミド、N−ビニルアセトアミド、N−ビニルピロリドン、N、N−ジメチルアクリルアミド、アクリロニトリル、ジアセトンアクリルアミド、2−ヒドロキシエチル(メタ)アクリレート等であるが、アクリルアミドとの共重合体が好ましい。又、その他のカチオン性単量体、例えば、(メタ)アクリロイルオキシエチルトリメチルアンモニウム塩化物などを高分子分散剤組成中に含有していても差し支えない。 In the present invention, the polymer dispersant used for the salt water dispersion polymerization is one containing diallyldimethylammonium chloride as a structural unit. Polydiallyldimethylammonium chloride may be used, but a copolymer of diallyldimethylammonium chloride and a nonionic monomer can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, acrylonitrile, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, etc. However, a copolymer with acrylamide is preferred. In addition, other cationic monomers such as (meth) acryloyloxyethyltrimethylammonium chloride may be contained in the polymer dispersant composition.
前記高分子分散剤の分子量としては、高いと分散液の粘性が高くなり好ましくない。従って5,000〜200万、好ましくは5万〜100万である。高分子分散剤の添加率は、単量体に対して1〜20質量%であり、好ましくは5〜20質量%である。分散液に対して5質量%未満が好ましい。これは5質量%以上含有すると経済的に不利であり、高分子の機能を阻害する可能性が有るためである。 When the molecular weight of the polymer dispersant is high, the viscosity of the dispersion becomes high, which is not preferable. Therefore, it is 5,000 to 2,000,000, preferably 50,000 to 1,000,000. The addition rate of a polymer dispersing agent is 1-20 mass% with respect to a monomer, Preferably it is 5-20 mass%. The amount is preferably less than 5% by mass with respect to the dispersion. This is because containing 5% by mass or more is economically disadvantageous and may inhibit the function of the polymer.
重合時に使用する無機塩としては、塩化物イオンと多価アニオンを含有する塩を使用する。この二種類の塩を必須として使用することで大きな増粘を抑制し、且つ無機塩総量を減少させた水溶性重合体分散液を製造することができる。塩化物イオンを含有する塩として、塩化ナトリウム、塩化カリウム、塩化カルシウム、等が挙げられる。多価アニオンを含有する塩として、硫酸ナトリウム、硫酸マグネシウムが好ましい。塩化物イオン含有塩と多価アニオン含有塩の比率は、質量比で1:9〜9:1の範囲であり、好ましくは3:7〜7:3である。これら以外のアルカリ金属イオン、ハロゲン化物イオン、硝酸イオン、リン酸イオン、アンモニウムイオン等も含まれていても良い。これら無機塩水溶液中に前記単量体類を溶解させ、更に高分子分散剤を共存させ、pHを2〜5に調製した後、窒素置換後、重合開始剤によって重合を開始させる。 As the inorganic salt used at the time of polymerization, a salt containing a chloride ion and a polyvalent anion is used. By using these two types of salts as essential, it is possible to produce a water-soluble polymer dispersion in which a large viscosity is suppressed and the total amount of inorganic salts is reduced. Examples of the salt containing chloride ions include sodium chloride, potassium chloride, calcium chloride and the like. As a salt containing a polyvalent anion, sodium sulfate and magnesium sulfate are preferable. The ratio of the chloride ion-containing salt to the polyvalent anion-containing salt is in the range of 1: 9 to 9: 1 by mass ratio, preferably 3: 7 to 7: 3. Alkali metal ions, halide ions, nitrate ions, phosphate ions, ammonium ions and the like other than these may also be included. The monomers are dissolved in these inorganic salt aqueous solutions, a polymer dispersant is further allowed to coexist, the pH is adjusted to 2 to 5, and after substitution with nitrogen, polymerization is initiated by a polymerization initiator.
塩化物イオンと多価アニオンを併用すると無機塩の総量を減らすことができ、水溶性重合体分散液総量に対して、15質量%未満にすることができる。通常は20質量%以上存在しないと安定した分散液は製造できない。これは製造時に大きな増粘が生じるためである。しかし、本発明では、構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を使用し、塩化物イオンと多価アニオンを併用することで増粘を抑制し、且つ無機塩総量を15質量%未満に減少できることを見出し本発明に至った。 When chloride ions and polyvalent anions are used in combination, the total amount of inorganic salts can be reduced, and the total amount of water-soluble polymer dispersion can be reduced to less than 15% by mass. Usually, a stable dispersion cannot be produced unless it is present in an amount of 20% by mass or more. This is because large thickening occurs during production. However, in the present invention, a polymer dispersing agent containing diallyldimethylammonium chloride as a structural unit is used, thickening is suppressed by using chloride ions and polyvalent anions in combination, and the total amount of inorganic salts is 15 mass. As a result, the present invention was found.
構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤と、塩化物イオンと多価アニオンを併用すると増粘を抑制する効果があることについては、理論的には不明な部分が多く解明できないが、現象面から推定すると以下の様になる。即ち、塩水溶液中で重合が進行していくと、生成高分子濃度は、溶解度以上となり高分子粒子の析出が始まるが、その手前では溶解している高分子のため重合物自体(重合系)の粘性も増加し、溶解高分子と析出粒子が共存した状態になる。この後、析出した高分子の割合は増加していき、重合物は徐々に粘性が低下し、分散状態に相変化する。この共存状態時に、析出粒子とゲル状の溶解高分子間における滑りを向上させ、相変化前の増粘状態から分散状態への相変化をスムーズに移行させるのが、相移行期における分散剤の主な役目と考えられる。重合の初期段階では、分散剤の構成単位であるジアリルジメチルアンモニウム塩化物と塩化物イオンの作用により、生成高分子の比較的低分子量の相分離に関与し、相変化を円滑に進行させ、重合の後半では塩析力の強い多価アニオンの作用により生成高分子の比較的高分子量のものとの塩析効果を促進する結果、高分子分散液が安定して製造できると考えられる。 Theoretically, there are many unclear points about the fact that the use of a polymeric dispersant containing diallyldimethylammonium chloride as a structural unit and the combined use of chloride ions and polyvalent anions has the effect of suppressing thickening. However, it is as follows when estimated from the phenomenon side. That is, as polymerization proceeds in an aqueous salt solution, the concentration of the produced polymer becomes higher than the solubility, and precipitation of polymer particles begins, but the polymer itself (polymerization system) because of the dissolved polymer before that. The viscosity of the polymer also increases, and the dissolved polymer and precipitated particles coexist. Thereafter, the ratio of the precipitated polymer increases, the viscosity of the polymer gradually decreases, and changes into a dispersed state. In this coexisting state, the slip between the precipitated particles and the gel-like dissolved polymer is improved, and the phase transition from the thickened state before the phase change to the dispersed state smoothly shifts. It is considered the main role. In the initial stage of polymerization, due to the action of diallyldimethylammonium chloride, which is a constituent unit of the dispersant, and chloride ions, it participates in the phase separation of the resulting polymer with a relatively low molecular weight, allowing the phase change to proceed smoothly. In the latter half of the process, it is considered that the polymer dispersion can be stably produced as a result of promoting the salting out effect of the produced polymer with a relatively high molecular weight by the action of the polyvalent anion having a strong salting out power.
本発明において、有効成分として作用せず、又、高分子の機能を阻害する場合がある無機塩を抑制することができる。特に水溶性重合体分散液の無機塩として、一般的に硫酸アンモニウムが好適に使用されているが、硫酸アンモニウム塩由来の全窒素含有量は、50000ppm(対水溶性重合体分散液製品)程度は含まれている。この硫酸アンモニウム塩由来の窒素を無くすことで、全窒素含有量を30000ppm(対水溶性重合体分散液製品)未満にまで低減することができる。全窒素含有量は、農作物に対して大きな影響力をもつ。植物はアンモニウム態窒素又は硝酸態窒素の形で窒素を吸収してその生育に利用されるが、窒素過多になるとかえって悪影響を与えることが知られており、含有量の低減が求められている。又、平成26年の水質汚濁防止法改正に伴いアンモニウム化合物が有害物質に指定されていることから環境に与える影響が懸念されており、本発明の水溶性重合体分散液は、無機塩総量を15質量%未満に抑制できるので環境に与える影響も大幅に減少させることができるものである。 In the present invention, an inorganic salt that does not act as an active ingredient and may inhibit the function of the polymer can be suppressed. In particular, ammonium sulfate is preferably used as the inorganic salt of the water-soluble polymer dispersion, but the total nitrogen content derived from the ammonium sulfate salt is about 50,000 ppm (for water-soluble polymer dispersion products). ing. By eliminating the nitrogen derived from the ammonium sulfate salt, the total nitrogen content can be reduced to less than 30000 ppm (for a water-soluble polymer dispersion product). Total nitrogen content has a great influence on crops. Plants absorb nitrogen in the form of ammonium nitrogen or nitrate nitrogen and are used for its growth. However, it is known that excessive nitrogen causes adverse effects, and a reduction in the content is required. In addition, since the ammonium compound is designated as a hazardous substance in accordance with the revision of the Water Pollution Control Law in 2014, there is a concern about the impact on the environment. The water-soluble polymer dispersion of the present invention has a total amount of inorganic salts. Since it can be suppressed to less than 15% by mass, the influence on the environment can be greatly reduced.
重合濃度としては、単量体濃度として10質量%〜35質量%であるが、好ましくは15質量%〜30質量%である。これは単量体濃度が高い程、輸送コストの問題で経済的に有利であるが、単量体濃度が35質量%を超えると製造時に増粘が大きくなり分散液が得られ難くなるためである。単量体供給方法としては、重合開始時、一括して仕込んでも良いし、適宜分割して仕込んでも良い。 The polymerization concentration is 10% by mass to 35% by mass as the monomer concentration, and preferably 15% by mass to 30% by mass. This is because the higher the monomer concentration, the more economically advantageous due to the problem of transportation costs. However, if the monomer concentration exceeds 35% by mass, the viscosity increases during production and it becomes difficult to obtain a dispersion. is there. As a monomer supply method, it may be charged all at once at the start of polymerization, or may be charged in an appropriate manner.
重合条件は通常、使用する単量体や共重合モル%によって適宜決定し、温度としては0〜100℃の範囲で行う。重合開始はラジカル重合開始剤を使用する。これら開始剤は油溶性あるいは水溶性のどちらでも良く、アゾ系、過酸化物系、レドックス系の何れでも重合することが可能である。油溶性アゾ系開始剤の例としては、2、2’−アゾビスイソブチロニトリル、1、1’−アゾビス(シクロヘキサンカルボニトリル)、2、2’−アゾビス(2−メチルブチロニトリル)、2、2’−アゾビス(2−メチルプロピオネート)、4、4−アゾビス(4−メトキシ−2、4ジメチル)バレロニトリル等が挙げられ、水混溶性溶剤に溶解し添加する。 The polymerization conditions are usually determined appropriately depending on the monomers used and the copolymerization mol%, and the temperature is in the range of 0 to 100 ° C. For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile, and the like are mentioned, which are dissolved in a water-miscible solvent and added.
水溶性アゾ系開始剤の例としては、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩、2、2’−アゾビス[2−(2−アミジノプロパン)二塩酸塩、4、4’−アゾビス(4−シアノ吉草酸)等が挙げられる。又、レドックス系の例としては、ペルオクソ二硫酸アンモニウムと亜硫酸ナトリウム、亜硫酸水素ナトリウム、トリメチルアミン、テトラメチルエチレンジアミン等との組み合わせが挙げられる。更に過酸化物の例としては、ペルオクソ二硫酸アンモニウム或いはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイド、オクタノイルペルオキサイド、サクシニックペルオキサイド、t−ブチルペルオキシ2−エチルヘキサノエート等を挙げることができる。これら開始剤の中で最も好ましいのは、水溶性アゾ開始剤の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩、2、2’−アゾビス[2−(2−アミジノプロパン)二塩酸塩である。アゾ系開始剤の添加量は、重合開始時、単量体当たり50〜500ppm、好ましくは70〜200ppm添加する。しかし、一回の添加では重合率が低くなるので、数回に分けて添加することが好ましい。 Examples of water-soluble azo initiators include 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-amidinopropane) And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of the redox system include a combination of ammonium peroxodisulfate and sodium sulfite, sodium bisulfite, trimethylamine, tetramethylethylenediamine and the like. Further examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate, and the like. be able to. Most preferred among these initiators is the water-soluble azo initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-Amidinopropane) dihydrochloride. The addition amount of the azo initiator is 50 to 500 ppm, preferably 70 to 200 ppm per monomer at the start of polymerization. However, since the polymerization rate is lowered by a single addition, it is preferable to add in several portions.
又、レドックス系開始剤で共重合する場合、40℃以上の条件で重合を開始させると重合の制御は難しく、急激な温度上昇や重合液の塊状化などが起きて、高重合度で安定な分散液が得られないため、15〜35℃が好ましい。この開始剤の添加率は、重合開始時、単量体当たり5〜100ppm、好ましくは10〜50ppm添加する。しかし、一回の添加では重合率が低くなるので、数回添加することが好ましい。添加回数としては、2〜5回、好ましくは2〜3回である。これらイオン性高分子からなる高分子分散剤の添加量としては、対単量体1〜30質量%であり、好ましくは2〜20質量%である。1質量%以下では、分散剤としての効果がなく、30質量%以上では、分散液の粘性が高くなる上、コスト的に不利になる。 In addition, when copolymerizing with a redox initiator, it is difficult to control the polymerization when the polymerization is started at a temperature of 40 ° C. or more, and a rapid temperature rise or agglomeration of the polymerization solution occurs, resulting in a high degree of polymerization and stability. Since a dispersion liquid cannot be obtained, 15-35 degreeC is preferable. The initiator is added at a rate of 5 to 100 ppm, preferably 10 to 50 ppm per monomer at the start of polymerization. However, since the polymerization rate is lowered by a single addition, it is preferably added several times. As addition frequency, it is 2-5 times, Preferably it is 2-3 times. The addition amount of the polymer dispersant composed of these ionic polymers is 1 to 30% by mass, preferably 2 to 20% by mass with respect to the monomer. If it is 1% by mass or less, there is no effect as a dispersing agent, and if it is 30% by mass or more, the viscosity of the dispersion becomes high and the cost becomes disadvantageous.
本発明における水溶性重合体分散液は、都市下水、屎尿、一般産業排水の生汚泥、余剰汚泥、凝集汚泥、消化汚泥あるいはこれらの混合汚泥を凝集処理する際、またはデカンター、ベルトプレス、フィルタープレス、スクリュウプレス脱水機などで凝集脱水する際に添加する薬剤、製油工程あるいは油分を含む産業排水の油分離工程および処理に用いる油分離剤、製紙工程に用いる濾水性向上剤、歩留向上剤、白水中の有価物回収剤等の製紙用薬剤等として使用でき、これらの用途として機能を発揮するためには、本発明における水溶性重合体分散液の分子量の指標となる0.5質量%塩水溶液粘度、即ち、分散液を構成する水溶性重合体の25℃で測定した0.5質量%における、2質量%硫酸アンモニウム水溶液中の水溶液粘度が5〜150mPa・sの範囲であり、20〜150mPa・sが好ましい。4質量%塩化ナトリウム水溶液中の水溶液粘度では5〜150mPa・sの範囲であり、15〜150mPa・sが好ましい。 The water-soluble polymer dispersion in the present invention is used for agglomeration treatment of municipal sewage, human waste, raw sludge from general industrial wastewater, surplus sludge, agglomerated sludge, digested sludge, or mixed sludges thereof, or a decanter, belt press, filter press. , Chemicals added when coagulating and dewatering with a screw press dehydrator, etc., oil separation process or oil separation process used in industrial wastewater containing oil, and oil separation agent used in processing, drainage improver used in papermaking process, yield improver, 0.5 mass% salt which can be used as a papermaking agent such as a valuable material recovery agent in white water and serves as an index of the molecular weight of the water-soluble polymer dispersion in the present invention in order to exert its function as these uses The aqueous solution viscosity, i.e., the aqueous solution viscosity in a 2 mass% ammonium sulfate aqueous solution at 0.5 mass% measured at 25C of the water-soluble polymer constituting the dispersion is 5 to 1 It is in the range of 0mPa · s, 20~150mPa · s is preferable. The aqueous solution viscosity in a 4% by mass sodium chloride aqueous solution is in the range of 5 to 150 mPa · s, and preferably 15 to 150 mPa · s.
以下に本発明における水溶性重合体分散液及びその製造方法について具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The water-soluble polymer dispersion and the method for producing the same according to the present invention will be specifically described below, but the present invention is not limited to the following examples.
(製造例1)アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水154.2g、35質量%ポリジアリルジメチルアンモニウム塩化物20.5g、更に塩化ナトリウム11.1g、硫酸ナトリウム4.5gを加え、撹拌下40℃に昇温し均一に溶解した。次に、50質量%アクリルアミド41.7g、80質量%アクリロイルオキシエチルトリメチルアンモニウム塩化物10.9g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物38gを加え均一溶液とし、40℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり200ppm添加し、撹拌下40℃で18時間重合した。反応終了後、得られた分散液に硫酸ナトリウム18gを加え硫酸ナトリウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド/アクリロイルオキシエチルトリメチルアンモニウム塩化物/アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物=65/10/25モル%となる。この分散液の粘度は526mPa・sで、2質量%硫酸アンモニウム水溶液に水溶性重合体分散液を0.5質量%濃度に溶かした時の粘度は85mPa・sであった。これを実施例1として表1に示す。この水溶性重合体分散液の全窒素含有量は理論値としては23587ppm(対分散液)となる。 (Production Example 1) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling tube and a nitrogen introduction tube, 154.2 g of demineralized water, 20.5 g of 35 mass% polydiallyldimethylammonium chloride, and sodium chloride 11 0.1 g and sodium sulfate 4.5 g were added, and the mixture was heated to 40 ° C. with stirring and dissolved uniformly. Next, 41.7 g of 50% by mass acrylamide, 10.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 38 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to make a homogeneous solution, and immersed in a 40 ° C. hot water bath. The temperature was stabilized. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was carried out at 40 ° C. for 18 hours. After completion of the reaction, 18 g of sodium sulfate was added to the obtained dispersion, and the mixture was stirred until the remaining sodium sulfate was not dissolved to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 65/10/25 mol%. The dispersion had a viscosity of 526 mPa · s, and the viscosity when the water-soluble polymer dispersion was dissolved in a 2% by mass aqueous ammonium sulfate solution at a concentration of 0.5% by mass was 85 mPa · s. This is shown in Table 1 as Example 1. The total nitrogen content of this water-soluble polymer dispersion is theoretically 23,87 ppm (vs. dispersion).
(製造例2)アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水139.2g、35質量%ポリジアリルジメチルアンモニウム塩化物32.4g、更に塩化ナトリウム6.3g、硫酸ナトリウム4.2gを加え、撹拌下40℃に昇温し均一に溶解した。次に、50質量%アクリルアミド24.6g、80質量%アクリロイルオキシエチルトリメチルアンモニウム塩化物20.9g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物58.2gを加え均一溶液とし、40℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり200ppm添加し、撹拌下40℃で18時間重合した。反応終了後、得られた分散液に硫酸ナトリウム14gを加え硫酸ナトリウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド/アクリロイルオキシエチルトリメチルアンモニウム塩化物/アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物=40/20/40モル%となる。この分散液は5460mPa・sで、2質量%硫酸アンモニウム水溶液に分散液を0.5質量%濃度に溶かした時の粘度は71mPa・sであった。これを実施例2として表1に示す。この水溶性重合体分散液の全窒素含有量は理論値として23448ppm(対分散液)となる。 (Production Example 2) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introducing pipe, 139.2 g of demineralized water, 32.4 g of 35% by mass polydiallyldimethylammonium chloride, and further sodium chloride 6 .3 g and sodium sulfate 4.2 g were added, and the mixture was heated to 40 ° C. with stirring and dissolved uniformly. Next, 24.6 g of 50% by mass acrylamide, 20.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 58.2 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to obtain a homogeneous solution, and a hot bath at 40 ° C. So as to stabilize the temperature. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was carried out at 40 ° C. for 18 hours. After the completion of the reaction, 14 g of sodium sulfate was added to the obtained dispersion, and the mixture was stirred until there was no undissolved sodium sulfate to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 40/20/40 mol%. This dispersion was 5460 mPa · s, and the viscosity when the dispersion was dissolved in a 2% by mass ammonium sulfate aqueous solution to a concentration of 0.5% by mass was 71 mPa · s. This is shown in Table 1 as Example 2. The total nitrogen content of this water-soluble polymer dispersion is 23448 ppm (vs. dispersion) as a theoretical value.
(製造例3)アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水156g、35質量%ポリジアリルジメチルアンモニウム塩化物25.7g、更に塩化ナトリウム14.8g、硫酸ナトリウム4.8gを加え、撹拌下40℃に昇温し均一に溶解した。次に、50質量%アクリルアミド63.3g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物16.7gを加え均一溶液とし、40℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり100ppm添加し、撹拌下40℃で18時間重合した。反応終了後、得られた分散液に硫酸ナトリウム18.7gを加え硫酸ナトリウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド/アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物=90/10モル%となる。この分散液は11600mPa・sで、4質量%塩化ナトリウム水溶液に分散液を0.5質量%濃度に溶かした時の粘度は52mPa・sであった。これを実施例3として表1に示す。この水溶性重合体分散液の全窒素含有量は理論値として25715ppm(対分散液)となる。 (Production Example 3) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introduction pipe, 156 g of demineralized water, 25.7 g of 35% by mass polydiallyldimethylammonium chloride, and further 14.8 g of sodium chloride 4.8 g of sodium sulfate was added, and the mixture was heated to 40 ° C. with stirring and dissolved uniformly. Next, 63.3 g of 50% by mass acrylamide and 16.7 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to obtain a homogeneous solution, which was then immersed in a 40 ° C. hot water bath to stabilize the temperature. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was added as a polymerization initiator at 100 ppm per monomer and stirred. Polymerization was carried out at 40 ° C. for 18 hours. After the completion of the reaction, 18.7 g of sodium sulfate was added to the obtained dispersion, and the mixture was stirred until the sodium sulfate remained undissolved to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyldimethylbenzylammonium chloride = 90/10 mol%. This dispersion was 11600 mPa · s, and the viscosity when the dispersion was dissolved in a 4% by mass sodium chloride aqueous solution to a concentration of 0.5% by mass was 52 mPa · s. This is shown in Table 1 as Example 3. The total nitrogen content of this water-soluble polymer dispersion is 25715 ppm (vs. dispersion) as a theoretical value.
(製造例4)アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水193.6g、35質量%ポリジアリルジメチルアンモニウム塩化物12.3g、更に塩化ナトリウム12.4g、硫酸マグネシウム4.9gを加え、撹拌下36℃に昇温し均一に溶解した。次に、50質量%アクリルアミド25.0g、80質量%アクリロイルオキシエチルトリメチルアンモニウム塩化物6.6g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物22.8gを加え均一溶液とし、36℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり80ppm添加し、撹拌下36℃で18時間重合した。反応終了後、得られた分散液に硫酸マグネシウム17.0gを加え硫酸マグネシウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド/アクリロイルオキシエチルトリメチルアンモニウム塩化物/アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物=65/10/25モル%となる。この分散液は425mPa・sで、2質量%硫酸アンモニウム水溶液に分散液を0.4質量%濃度に溶かした時の粘度は61mPa・sであった。これを実施例4として表1に示す。この水溶性重合体分散液の全窒素含有量は理論値として15131ppm(対分散液)となる。 (Production Example 4) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introduction pipe, 193.6 g of demineralized water, 12.3 g of 35% by mass polydiallyldimethylammonium chloride, and 12% of sodium chloride 0.4 g and magnesium sulfate 4.9 g were added, and the mixture was heated to 36 ° C. with stirring and dissolved uniformly. Next, 25.0 g of 50% by mass acrylamide, 6.6 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 22.8 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to form a homogeneous solution, and a 36 ° C. water bath So as to stabilize the temperature. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 80 ppm per monomer and stirred. Polymerization was carried out at 36 ° C. for 18 hours. After the completion of the reaction, 17.0 g of magnesium sulfate was added to the obtained dispersion, and the mixture was stirred until the magnesium sulfate was not dissolved to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 65/10/25 mol%. This dispersion was 425 mPa · s, and the viscosity when the dispersion was dissolved in a 2% by mass ammonium sulfate aqueous solution to a concentration of 0.4% by mass was 61 mPa · s. This is shown in Table 1 as Example 4. The total nitrogen content of this water-soluble polymer dispersion is 15131 ppm (vs. dispersion) as a theoretical value.
(比較製造例1)実施例1と同じ条件で、無機塩として硫酸ナトリウムのみを使用して製造した。アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水154.2g、35質量%ポリジアリルジメチルアンモニウム塩化物20.5g、更に硫酸ナトリウム15.5gを加え、撹拌下40℃に昇温し均一に溶解した。次に、50質量%アクリルアミド41.7g、80質量%アクリロイルオキシエチルトリメチルアンモニウム塩化物10.9g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物38gを加え均一溶液とし、40℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり200ppm添加し、撹拌下40℃で重合を開始した。反応途中、反応液の粘度が上昇し撹拌困難となり固化した。 (Comparative Production Example 1) Production was carried out under the same conditions as in Example 1 using only sodium sulfate as the inorganic salt. To a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introduction pipe, 154.2 g of demineralized water, 20.5 g of 35% by mass polydiallyldimethylammonium chloride, and 15.5 g of sodium sulfate were added. The temperature was raised to 40 ° C. with stirring, and the mixture was uniformly dissolved. Next, 41.7 g of 50% by mass acrylamide, 10.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 38 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to make a homogeneous solution, and immersed in a 40 ° C. hot water bath. The temperature was stabilized. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was started at 40 ° C. During the reaction, the viscosity of the reaction solution increased, making stirring difficult and solidifying.
(比較製造例2)実施例1と同じ条件で、高分子分散剤のポリジアリルジメチルアンモニウム塩化物をポリアクリロイルオキシエチルトリメチルアンモニウム塩化物に替えて製造した。アンカー翼撹拌機、冷却管及び窒素導入管を備えた0.5Lのセパラブルフラスコに脱塩水118g、20質量%ポリアクリロイルオキシエチルトリメチルアンモニウム塩化物56.7g、更に塩化ナトリウム11.1g、硫酸ナトリウム4.5gを加え、撹拌下40℃に昇温し均一に溶解した。次に、50質量%アクリルアミド41.7g、80質量%アクリロイルオキシエチルトリメチルアンモニウム塩化物10.9g、80質量%アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物38gを加え均一溶液とし、40℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、10質量%の2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩水溶液を重合開始剤として対単量体あたり200ppm添加し、撹拌下40℃で重合を開始した。反応途中、反応液の粘度が上昇し撹拌困難となり固化した。 (Comparative Production Example 2) Under the same conditions as in Example 1, the polymer dispersant polydiallyldimethylammonium chloride was produced in place of polyacryloyloxyethyltrimethylammonium chloride. In a 0.5 L separable flask equipped with an anchor blade stirrer, a condenser tube and a nitrogen inlet tube, 118 g of demineralized water, 56.7 g of 20% by mass polyacryloyloxyethyltrimethylammonium chloride, 11.1 g of sodium chloride, sodium sulfate 4.5g was added, and it heated up to 40 degreeC with stirring and melt | dissolved uniformly. Next, 41.7 g of 50% by mass acrylamide, 10.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 38 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to make a homogeneous solution, and immersed in a 40 ° C. hot water bath. The temperature was stabilized. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was started at 40 ° C. During the reaction, the viscosity of the reaction solution increased, making stirring difficult and solidifying.
(表1)
AAM:アクリルアミド
DMQ:アクリロイルオキシエチルトリメチルアンモニウム塩化物
DMBZ:アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物
高分子分散剤p−DD:ポリジアリルジメチルアンモニウム塩化物
高分子分散剤p−DMQ:ポリアクリロイルオキシエチルトリメチルアンモニウム塩化物
重合時塩:(a)塩化ナトリウム、(b)硫酸ナトリウム、(c)硫酸マグネシウム
単量体濃度:水溶性重合体分散液に対する単量体の質量割合
無機塩濃度:水溶性重合体分散液に対する無機塩の質量割合
分散液粘度:水溶性重合体分散液の25℃において測定した粘度
0.5質量%塩水溶液粘度:(実施例1、2、4)2質量%硫酸アンモニウム水中に高分子濃度が0.5質量%になるように溶解したときの25℃において測定した粘度、(実施例3)4質量%塩化ナトリウム水中に高分子濃度が0.5質量%になるように溶解したときの25℃において測定した粘度。
(Table 1)
AAM: acrylamide DMQ: acryloyloxyethyltrimethylammonium chloride DMBZ: acryloyloxyethyldimethylbenzylammonium chloride polymer dispersant p-DD: polydiallyldimethylammonium chloride polymer dispersant p-DMQ: polyacryloyloxyethyltrimethylammonium Salt during chloride polymerization: (a) sodium chloride, (b) sodium sulfate, (c) magnesium sulfate monomer concentration: mass ratio of monomer to water-soluble polymer dispersion inorganic salt concentration: water-soluble polymer dispersion Mass ratio of inorganic salt to liquid Dispersion viscosity: Viscosity of water-soluble polymer dispersion measured at 25 ° C. 0.5% by weight Salt aqueous solution viscosity: (Examples 1, 2, 4) Polymer in 2% by weight ammonium sulfate water To 25 ° C when dissolved to a concentration of 0.5% by mass There viscosity was measured, viscosity measured at 25 ° C. when dissolved as polymer concentration of 0.5 wt% (Example 3) 4% by weight sodium chloride in water.
高分子分散剤としてポリジアリルジメチルアンモニウム塩化物、無機塩として塩化物イオンと多価アニオンを使用して得られた水溶性重合体分散液の実施例1〜4においては、無機塩の総量が、8.1〜12.7質量%であり、無機塩の含有量が15質量%未満の低い水溶性重合体分散液である。無機塩として塩化ナトリウムを未使用の比較製造例1、及び構成単位としてジアリルジメチルアンモニウム塩化物を含有しない高分子分散剤を使用した比較製造例2では、分散液を製造することができなかった。構成単位として、ジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を使用し、無機塩として塩化物イオンと多価アニオンを併用することで、硫酸アンモニウムを使用しなくても増粘を抑制でき分散液が得られることが分かった。
In Examples 1 to 4 of water-soluble polymer dispersions obtained using polydiallyldimethylammonium chloride as a polymer dispersant and chloride ions and polyvalent anions as inorganic salts, the total amount of inorganic salts is: It is a low water-soluble polymer dispersion having a content of 8.1 to 12.7% by mass and an inorganic salt content of less than 15% by mass. In Comparative Production Example 1 in which sodium chloride was not used as an inorganic salt, and in Comparative Production Example 2 in which a polymer dispersant containing no diallyldimethylammonium chloride was used as a structural unit, a dispersion could not be produced. Using a polymer dispersant containing diallyldimethylammonium chloride as a structural unit, and using a chloride ion and a polyvalent anion together as an inorganic salt, the dispersion can be suppressed without using ammonium sulfate. Was found to be obtained.
Claims (4)
一般式(1)
R1は水素又はメチル基、R2、R3は炭素数1〜3のアルキル基、アルコキシ基、R4は炭素数7〜20のアルキル基あるいはアリール基である。Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基、X1は陰イオンをそれぞれ表わす。 In a salt aqueous solution containing a chloride ion and a polyvalent anion, a monomer or monomer mixture aqueous solution containing the monomer represented by the following general formula (1) as an essential component is constituted in the salt aqueous solution. A water-soluble polymer dispersion obtained by co-existing a polymer dispersant containing a polymer containing diallyldimethylammonium chloride as a unit, and dispersion polymerization under stirring, with respect to the total amount of the water-soluble polymer dispersion A water-soluble polymer dispersion, wherein the total amount of the inorganic salt is less than 15% by mass.
General formula (1)
R1 is hydrogen or a methyl group, R2 and R3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X1 represents an anion.
一般式(1)
R1は水素又はメチル基、R2、R3は炭素数1〜3のアルキル基、アルコキシ基、R4は炭素数7〜20のアルキル基あるいはアリール基である。Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基、X1は陰イオンをそれぞれ表わす。 In a salt aqueous solution containing a chloride ion and a polyvalent anion, a monomer or monomer mixture aqueous solution containing the monomer represented by the following general formula (1) as an essential component is constituted in the salt aqueous solution. A water-soluble polymer dispersion obtained by co-existing a polymer dispersant containing a polymer containing diallyldimethylammonium chloride as a unit, and dispersion polymerization under stirring, with respect to the total amount of the water-soluble polymer dispersion A method for producing a water-soluble polymer dispersion, wherein the total amount of the inorganic salt is less than 15% by mass.
General formula (1)
R1 is hydrogen or a methyl group, R2 and R3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X1 represents an anion.
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