JPH0446915A - Water-soluble polymer and paper-making additive - Google Patents
Water-soluble polymer and paper-making additiveInfo
- Publication number
- JPH0446915A JPH0446915A JP15824090A JP15824090A JPH0446915A JP H0446915 A JPH0446915 A JP H0446915A JP 15824090 A JP15824090 A JP 15824090A JP 15824090 A JP15824090 A JP 15824090A JP H0446915 A JPH0446915 A JP H0446915A
- Authority
- JP
- Japan
- Prior art keywords
- water
- component
- meth
- salt
- monomer
- 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.)
- Pending
Links
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 21
- 239000000654 additive Substances 0.000 title claims description 8
- 230000000996 additive effect Effects 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 42
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 8
- 239000003431 cross linking reagent Substances 0.000 abstract description 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- -1 alkali metal salts Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- DJLHXXNSHHGFLB-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C(C)=C DJLHXXNSHHGFLB-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- NWDCGICEHJVOPW-UHFFFAOYSA-N acetic acid;prop-2-enamide Chemical compound CC(O)=O.NC(=O)C=C NWDCGICEHJVOPW-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- HJWBBBADPXPUPA-UHFFFAOYSA-N ethyl 3-(4-chlorophenyl)-5-methyl-1,2-oxazole-4-carboxylate Chemical compound CCOC(=O)C1=C(C)ON=C1C1=CC=C(Cl)C=C1 HJWBBBADPXPUPA-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 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
- GJRKKTVFRGJAFQ-UHFFFAOYSA-N prop-2-en-1-ol;urea Chemical compound NC(N)=O.OCC=C GJRKKTVFRGJAFQ-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は製紙用添加剤として好適な水溶性ポリマー及び
、該水溶性ポリマーを主成分とする製紙用添加剤に関す
るものであって、特に高分子量でありながら、低粘度の
水溶液を形成する水溶性ポリマーに関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a water-soluble polymer suitable as a paper-making additive, and a paper-making additive containing the water-soluble polymer as a main component. However, it relates to water-soluble polymers that form aqueous solutions with low viscosity.
従来の技術
塗料や接着剤の分野においては、高分子Ｉで低粘度の水
溶性ポリマーは、塗布性能に優れているだけでなく、塗
膜性能にも優れている。また製紙用添加剤の分野では、
このようなポリマーは消泡性に優れていて使用し易いだ
けでなく、紙力増強効果に優れている。BACKGROUND OF THE INVENTION In the field of conventional coatings and adhesives, Polymer I, low viscosity, water-soluble polymers not only have excellent application performance but also excellent coating performance. In addition, in the field of papermaking additives,
Such polymers not only have excellent antifoaming properties and are easy to use, but also have excellent paper strength enhancement effects.
例えば製紙工業においては、省エネルギ一対策や環境対
策の一環として、製紙プロセスのクローズド化が進み、
それに伴い従来から使用されていた［酸バンドの添加率
も、おのずと制限されるようになっている。そこで、硫
酸バンドの低添加乃至無添加の場合においても、十分な
紙力効果を発現せしめるような薬剤の開発が望まれてい
るのである。For example, in the paper manufacturing industry, as part of energy saving and environmental measures, the paper manufacturing process is becoming increasingly closed.
Accordingly, the addition rate of the acid band, which has been conventionally used, has naturally become limited. Therefore, there is a demand for the development of a drug that can produce sufficient paper strength effects even when a small amount or no sulfuric acid is added.
かかる観点から、硫酸バンドのような定着剤の併用の有
無に拘らず、広範囲のｐＨ領域で使用可能な紙力増強剤
として、例えば特開昭５４−８０９１８号公報、特開昭
６０−９４６９７号公報などに示されるような、アクリ
ルアミドと、α、β不飽和モノカルボン酸又はジカルボ
ン酸と、ジメチルアミノエチルメタクリレートのような
塩基性モノマーとよりなる、両性の水溶性共重合体が提
案されている。From this point of view, as a paper strength enhancer that can be used in a wide pH range regardless of the presence or absence of a fixing agent such as sulfuric acid, for example, JP-A-54-80918 and JP-A-60-94697 have been proposed. As shown in publications, an amphoteric water-soluble copolymer consisting of acrylamide, an α,β unsaturated monocarboxylic acid or dicarboxylic acid, and a basic monomer such as dimethylaminoethyl methacrylate has been proposed. .
発明が解決しようとする問題点
この種のポリマーにおいては、組成面以外でも、分子構
造や分子量の違いによっても様々な異った特性を示すが
、高分子量化による改善は、急激な粘度の増加を伴い、
使用操作上の制約から高分子量化にも限界があった。Problems to be Solved by the Invention This type of polymer exhibits a variety of different properties not only in terms of composition but also due to differences in molecular structure and molecular weight. Accompanied by
There was also a limit to increasing the molecular weight due to operational constraints.
また従来、ＰＡＭ系ポリマーを高分子量化する方法とし
て、低固形分下において重合する方法や、多官能性ジビ
ニルモノマーにより架橋する方法（特開昭６３−５０５
９７号公報）などが知られているが、これらの方法では
重合条件設定の許容幅が限定され、重合反応のコントロ
ールが困龍である。Conventionally, methods for increasing the molecular weight of PAM-based polymers include a method of polymerizing under low solid content and a method of crosslinking with a polyfunctional divinyl monomer (Japanese Patent Laid-Open No. 63-505
97), but these methods have a limited tolerance for setting polymerization conditions, making it difficult to control the polymerization reaction.
本発明はかかる事情に鑑みなされたものであって、共重
合体中に疎水性モノマーを含ませることにより、固形分
を低下させることなく、高分子量で低粘度の水溶性ポリ
マーを得ることに成功したものである。The present invention was developed in view of the above circumstances, and by incorporating a hydrophobic monomer into the copolymer, it has succeeded in obtaining a water-soluble polymer with high molecular weight and low viscosity without reducing the solid content. This is what I did.
問題点を解決する手段
而して本発明は、（ａ）アクリルアミド及び／又はメタ
クリルアミドを７０〜９８．５モル％と、（ｂ）前記（
ａ）成分と共重合可能な水溶性アニオン性モノマー及び
／又はその塩を１〜２０モル％及び／又は、（ｃ）前記
（ａ）成分と共重合可能な水溶性カチオン性モノマー及
び／又はその塩を１〜２０モル％と、（ｄ）前記（ａ）
成分と共重合可能な疎水性モノマー及び／又はその塩を
０゜５〜１０モル％とを共重合してなることを特徴とす
る、水溶性ポリマー及び、該水溶性ポリマーを主成分と
する製紙用添加剤である。As a means to solve the problems, the present invention provides (a) 70 to 98.5 mol% of acrylamide and/or methacrylamide; (b) the above (
a) 1 to 20 mol% of a water-soluble anionic monomer and/or its salt copolymerizable with component (c) a water-soluble cationic monomer copolymerizable with component (a) and/or its salt; 1 to 20 mol% of salt; (d) the above (a);
A water-soluble polymer characterized by copolymerizing 0.5 to 10 mol % of a hydrophobic monomer and/or a salt thereof copolymerizable with a component, and a paper product containing the water-soluble polymer as a main component. It is an additive for
本発明においては、前記（ｄ）成分として、一般構造式
（Ｒ，、Ｒ，：水素又は低級アルキル基）で示されるス
チレン誘導体を使用することが好ましい。In the present invention, it is preferable to use a styrene derivative represented by the general structural formula (R, , R,: hydrogen or lower alkyl group) as the component (d).
また水溶性ポリマーの重合に当って、架橋剤を０．０１
〜２モル％使用して共重合したしのが好ましい。In addition, when polymerizing water-soluble polymers, add 0.01% of the crosslinking agent.
It is preferable to copolymerize using ~2 mol%.
本発明における水溶性ポリマーは、前述のように、＜ａ
）、（ｂ）、（ｃ）及び（ｄ）の四成分のモノマーより
なっている。As mentioned above, the water-soluble polymer in the present invention is <a
), (b), (c) and (d).
（ａ）成分としては、アクリルアミド及び／又はメタク
リルアミドが使用される。（ａ）成分は水溶性ポリマー
の主要成分であって、７０〜９８゜５モル％使用される
。As component (a), acrylamide and/or methacrylamide is used. Component (a) is the main component of the water-soluble polymer and is used in an amount of 70 to 98.5 mol %.
（ｂ）成分は、前記（ａ）成分と共重合可能な水溶性ア
ニオン性モノマー及び／又はその塩であって、α、β−
不飽和モノ及び／又はジカルボン酸及び／又はその塩類
が使用される。Component (b) is a water-soluble anionic monomer copolymerizable with component (a) and/or a salt thereof, which is α,β-
Unsaturated mono- and/or dicarboxylic acids and/or their salts are used.
α、β−不飽和モノカルボン酸の例としては、アクリル
酸、メタクリル酸、クロトン酸などが挙げられ、α、β
−不飽和ジカルボン敢の例としては、マレイン酸、無水
マレイン酸、フマル酸、イタコン酸、無水イタコン酸、
シトラコン酸などが挙げられる。Examples of α,β-unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, etc.
- Examples of unsaturated dicarboxylic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,
Examples include citraconic acid.
また（ｂ）成分として、（メタ）アクロイルオキシアル
キルホスフェイトなどの燐酸基含有モノマーを使用する
こともできる。Further, as the component (b), a phosphoric acid group-containing monomer such as (meth)acryloyloxyalkyl phosphate can also be used.
さらに（ｂ）成分としては、これらのモノマーの、アル
カリ金属塩、アルカリ土類金属塩、アミン塩、アンモニ
ウム塩などの塩類を使用することもできる。Further, as the component (b), salts of these monomers such as alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salts can also be used.
（ｃ）成分は、前記＜ａ）成分と共重合可能な水溶性カ
チオン牲モノマー及び／又はその塩である。Component (c) is a water-soluble cationic monomer copolymerizable with component <a) and/or a salt thereof.
水溶性カチオン性モノマーとしては、第三級アミノ基を
有する塩基性モノマーが適当であり、その例としては、
ジメチルアミノエチル（メタ）アクリレート、ジエチル
アミノエチル（メタ）アクリレート、ジメチルアミノプ
ロピル（メタ）アクリレート、ジエチルアミンプロピル
（メタ）アクリレート、ジメチルアミンエチル（メタ）
アクリルアミド、ジエチルアミノエチル（メタ）アクリ
ルアミド、ジメチルアミノプロピル（メタ）アクリルア
ミド、ジエチルアミノプロビル（メタ）アクリルアミド
が挙げられる。As the water-soluble cationic monomer, basic monomers having a tertiary amino group are suitable; examples thereof include:
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminepropyl (meth)acrylate, dimethylamineethyl (meth)
Examples include acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide.
またこれらの塩基性モノマーと無機又は有ｍ酸との塩類
を使用することもできる。It is also possible to use salts of these basic monomers and inorganic or organic acids.
さらに前記塩基性モノマーの、塩化メチル、塩化ベンジ
ル、ジエチル硫酸、ジエチル硫酸、エピクロルヒドリン
などの四級化剤との反応によって得られる第四級アンモ
ニウム塩や、ジメチルジアリルアンモニウムクロライド
などを使用することもできる。Furthermore, quaternary ammonium salts obtained by reacting the basic monomer with a quaternizing agent such as methyl chloride, benzyl chloride, diethyl sulfate, diethyl sulfate, and epichlorohydrin, dimethyl diallylammonium chloride, etc. can also be used. .
（ｂ）成分と（ｃ）成分とは、そのいずれかを使用すれ
ばよく、両者を併用することもできる。Either the component (b) or the component (c) may be used, or both can be used in combination.
その使用量は１〜２０モル％とすべきであり、特に２〜
１５モル％とするのが最適である。The amount used should be between 1 and 20 mol%, especially between 2 and 20% by mole.
The optimum content is 15 mol%.
次に（ｄ）成分は、前記（ａ）成分と共重合可能な疎水
性モノマー及び／又はその塩である。この（ｄ）成分の
使用量は０．５〜１０モル％とすべきであり、特に１〜
５モル％とするのが最適である。Next, component (d) is a hydrophobic monomer copolymerizable with component (a) and/or a salt thereof. The amount of component (d) used should be 0.5 to 10 mol%, especially 1 to 10% by mole.
The optimum content is 5 mol%.
この（ｄ）成分としては、−殻構造式
−ａ梢造式
（Ｒ１、Ｒ２：水素スは低級アルキル基）で示されるス
チレン又はその誘導体であることが好ましい、その具体
的な例としては、スチレン、α−メチルスチレン、ビニ
ルトルエンなどが挙げられる。The component (d) is preferably styrene or a derivative thereof represented by the -shell structure formula -a-shell structure formula (R1, R2: hydrogen is a lower alkyl group), and specific examples thereof include: Examples include styrene, α-methylstyrene, and vinyltoluene.
その他の疎水性モノマーの例としては、メチル（メタ）
アクリレート、エチル（メタ）アクリレート、ブチル（
メタ）アクリレート、２−エチルヘキシル（メタ）アク
リレート、ヒトｏ−ｉジエチル（メタ）アクリレート、
ヒドロキシプロピル（メタ）アクリレート、ヒドロキシ
ブチル（メタ）アクリレートなどのアクリル酸又はメタ
クリル酸のエステル類、酢酸ビニル、１０ピオン酸ビニ
ルなどのビニルエステル類、メチルビニルエーテル、エ
チルビニルエーテルなどのビニルエーテル類、Ｎ−メチ
ロール（メタ）アクリルアミド、Ｎ−アル書ル置換（メ
タ）アクリルアミド、ジアセトン（メタ）アクリルアミ
ドなどのアクリルアミド系モノマー、アクリロニトリル
、ビニルピロリドンなどが埜げられる。Examples of other hydrophobic monomers include methyl (meth)
Acrylate, ethyl (meth)acrylate, butyl (
meth)acrylate, 2-ethylhexyl(meth)acrylate, human o-i diethyl(meth)acrylate,
Acrylic acid or methacrylic acid esters such as hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate, vinyl esters such as vinyl acetate and vinyl 10 pionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, N-methylol Examples include acrylamide monomers such as (meth)acrylamide, N-alkyl-substituted (meth)acrylamide, and diacetone (meth)acrylamide, acrylonitrile, and vinylpyrrolidone.
以上に述べた（ａ）、（ｂ）、（ｃ）、（ｄ）に挙げた
四つの成分の他に、要求されるポリマー水溶液の性質に
応じて、（ｅ）前記（ａ）成分と共重合可能な架橋剤や
、（ｆ）反応性モノマーなとの、各種のモノマー成分を
付加して共重合することができる。In addition to the four components (a), (b), (c), and (d) mentioned above, depending on the required properties of the polymer aqueous solution, (e) Copolymerization can be carried out by adding various monomer components such as a polymerizable crosslinking agent and (f) a reactive monomer.
（ｅ）成分の架橋剤は共重合体の分子量を高くする作用
があり、ジ又はトリとニルモノマー系架橋剤が適当であ
る。The crosslinking agent (e) has the effect of increasing the molecular weight of the copolymer, and di- or tri-monomer-based crosslinking agents are suitable.
ジビニルモノマーとしては、メチレンビス（メタ）アク
リルアミド、エチレンビス（メタ）アクリルアミド、ヘ
キサメチレンビス（メタ）アクリルアミド、ビス（メタ
）アクリルアミド酢酸、ビス（メタ）アクリルアミド−
グリオキザール付加体、ビス（メタ）アクリルアミド−
メチロールエチレン尿素縮合体、ビス（メタ）アクリル
アミドメチロール尿素などのビス（メタ）アクリルアミ
ド類や、エチレングリコールジ（メタ）アクリレート、
ジエチレングリコールジ（メタ）アクリレート、トリエ
チレングリコール（メタ）アクリレートなどのジ（メタ
）アクリレート類、アジピン酸ジビニル、セバシン酸ジ
ビニルなどのジビニルエステル類、エポキシアクリレー
ト類、ウレタンアクリレート類などが適当である。Divinyl monomers include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, hexamethylene bis (meth) acrylamide, bis (meth) acrylamide acetic acid, and bis (meth) acrylamide.
Glyoxal adduct, bis(meth)acrylamide
Bis(meth)acrylamides such as methylolethylene urea condensate, bis(meth)acrylamide methylolurea, ethylene glycol di(meth)acrylate,
Di(meth)acrylates such as diethylene glycol di(meth)acrylate and triethylene glycol (meth)acrylate, divinyl esters such as divinyl adipate and divinyl sebacate, epoxy acrylates, and urethane acrylates are suitable.
トリビニルモノマーとしては、Ｎ、Ｎ−ジアリルアクリ
ルアミド、１，２．３−）リアクロイルへキサヒドロ−
８−トリアジン、トリアリルイソシアヌレートなどを挙
げることができる。Trivinyl monomers include N,N-diallylacrylamide, 1,2.3-)liacroylhexahydro-
Examples include 8-triazine and triallyl isocyanurate.
（ｅ）成分の架橋剤の添加量は、０，０１〜２モル％で
、好ましくは０．０２〜１モル％が最適である。The amount of the crosslinking agent (e) added is 0.01 to 2 mol%, preferably 0.02 to 1 mol%.
また（ｆ）成分の反応性モノマーとしては、メチロール
アクリルアミド、メトキシメチルアクリルアミド、メチ
ロールメタクリルアミド、エトキシメチルアクリルアミ
ド、グリシジルメタクリレートなどを使用することがで
きる。Further, as the reactive monomer of component (f), methylol acrylamide, methoxymethyl acrylamide, methylol methacrylamide, ethoxymethyl acrylamide, glycidyl methacrylate, etc. can be used.
さらにこれらの外、前記（ａ）成分と共重合し得るノニ
オン性モノマーを、重合物の水溶性を阻害しない程度に
加えることもできる。Furthermore, in addition to these, a nonionic monomer copolymerizable with the component (a) may be added to an extent that does not inhibit the water solubility of the polymer.
これらの各成分を共重合させるには、目的に応じたポリ
マー組成に適合した（ａ）、（ｂ）及び（ｃ）成分の混
合水溶液に、（ｄ）成分を加え、さらに必要に応じて（
ｅ）及び＜ｆ）成分を添加し、触媒を添加して重合を行
う。To copolymerize these components, component (d) is added to a mixed aqueous solution of components (a), (b), and (c) that is compatible with the polymer composition depending on the purpose, and if necessary, (
Components e) and <f) are added, a catalyst is added, and polymerization is carried out.
（ｄ）成分の種類や添加量によっては、重合後に相当量
のモノマーが残存する場合があり、このときには最高温
度到達後、さらに触媒を投入して重合する
重合触媒としては、ラジカル重合又はレドックス重合に
使用される酸化剤が使用可能である０例えば、過硫酸ア
ンモニウムや、過硫酸カリウムが適当である。(d) Depending on the type and amount of components added, a considerable amount of monomer may remain after polymerization. In this case, after the maximum temperature is reached, a catalyst is further added for polymerization. As a polymerization catalyst, radical polymerization or redox polymerization is recommended. For example, ammonium persulfate and potassium persulfate are suitable.
触媒の使用量は、モノマーの総量に対して、０゜０１〜
０．５重量％が適当であり、さらに好ましくは０．１〜
０．３１１量％程度とするのがｉ適である。The amount of catalyst used is 0°01 to 0.01 to the total amount of monomers.
0.5% by weight is appropriate, more preferably 0.1~
A suitable amount is about 0.311% by weight.
また分子量を調整するために、メルカプトエタノール、
チオ尿素、チオグリコール酸、メルカプトプロピオン酸
、チオサリチル酸、アミノエタンチオール、チオグリセ
ロール、チオリンゴ酸などのメルカプト系、アリルアル
コール、アリルスルホン酸ソーダ、アリルアミン、アリ
ルジメチルアミンなどのアリル系”、イソプロピルアル
コール、ペンタノールなどのアルコール系の連鎖移動側
を使用することができる。In addition, in order to adjust the molecular weight, mercaptoethanol,
Mercapto-types such as thiourea, thioglycolic acid, mercaptopropionic acid, thiosalicylic acid, aminoethanethiol, thioglycerol, and thiomalic acid, allyl-types such as allyl alcohol, sodium allylsulfonate, allylamine, and allyldimethylamine, isopropyl alcohol, An alcoholic chain transfer side such as pentanol can be used.
作用
本発明によれば、水溶性ポリマーは高分子量であり、し
かも水溶濯として十分な固形分濃度を有するにも拘らず
、低粘度で極めて取扱い易いしのとなる。According to the present invention, the water-soluble polymer has a high molecular weight and has a solid content concentration sufficient for use as a water-soluble polymer, yet has a low viscosity and is extremely easy to handle.
本発明の水溶性ポリマーが高分子量であり且つ低粘度を
示す理由については、現在のところ必ずしも明らかでは
ないが、概路次のような理由ではないかと考えられる。The reason why the water-soluble polymer of the present invention has a high molecular weight and a low viscosity is not necessarily clear at present, but it is thought that the reason may be as follows.
すなわち、疎水性モノマーの相互作用によりポリマー鎖
の空間的な拡がりが抑制され、比較的狭い空間内で密な
構造を取り、ポリマー鎖同士の絡み合いが少いため、分
子量が大きい割に粘度が低くなるものと考えられる。In other words, the interaction of hydrophobic monomers suppresses the spatial spread of polymer chains, forming a dense structure within a relatively narrow space, and there is little entanglement between polymer chains, resulting in a low viscosity despite its large molecular weight. considered to be a thing.
疎水性モノマーとして、芳香族系のものが有効であるの
も、芳香族系モノマーの疎水基は脂肪族系の疎水基に比
べて会合し易く、密な構造を取り易いため、少量でも有
効に作用するものと考えられる。Aromatic monomers are effective as hydrophobic monomers because the hydrophobic groups of aromatic monomers tend to associate more easily and form a dense structure than aliphatic hydrophobic groups, so they can be effective even in small amounts. It is thought that it works.
実施例
実施例１
攪拌機、温度計、還流冷却管及び窒素ガス導入管を備え
た四ツ目フラスコに、水２８０１；ｌ 、４０％アクリ
ルアミド水溶ｊ？ｔ１３９．２ｇ、６０％アクリル酸水
溶＞ｉ６．５ｇ、ジメチルアミノエチルメタクリレート
５．７ｇ及びスチレン２．８ｇを仕込み、１５％硫酸水
溶液でＩ）Ｈ４，Ｏに調節した後、窒素ガスを導入して
、反応系中の酸素を除去した。Examples Example 1 Into a four-eye flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 2801 l of water and 40% acrylamide in water were added. t139.2g, 60% acrylic acid aqueous solution>i6.5g, dimethylaminoethyl methacrylate 5.7g and styrene 2.8g were prepared, and after adjusting to I)H4,O with a 15% sulfuric acid aqueous solution, nitrogen gas was introduced. , oxygen in the reaction system was removed.
次いで５５°Ｃに昇温して、触媒としてイソプロピルア
ルコール０．５ｇ、過硫酸アンモニウム０１５ｇ及び亜
硫Ｍナトリウム０．０４ｇを投入し、重合を開始した０
反応により発熱して９３°Ｃまで昇温して、発熱は停止
した。Next, the temperature was raised to 55°C, and 0.5 g of isopropyl alcohol, 0.15 g of ammonium persulfate, and 0.04 g of sodium sulfite were added as catalysts to initiate polymerization.
The reaction generated heat and the temperature rose to 93°C, and then the heat generation stopped.
５分後に過硫酸アンモニウム０．０４ｏを投入し、６０
分間８５℃以上に保温して、重合を停止させて共重合体
水溶液を得た。After 5 minutes, add 0.04o ammonium persulfate and
The polymerization was stopped by keeping the temperature at 85° C. or higher for minutes to obtain an aqueous copolymer solution.
実施例２
実施例１において述べたと同じ四ツ目フラスコに水２８
５Ｑ 、４０％アクリルアミド水溶液１３１゜２ｇ、６
０％アクリル酸水溶液６．５１１１、イタコン酸２．３
ｇ、ジメチルアミノエチルメタクリレート１１．３（Ｊ
及びα−メチルスチレン２゜１ｇを仕込み、１５％硫酸
水溶液でｐＨ４，０に調節した後、窒素ガスを導入して
、反応系中の酸素を除去した。Example 2 Into the same four-eye flask as described in Example 1, 28 g of water was added.
5Q, 40% acrylamide aqueous solution 131°2g, 6
0% acrylic acid aqueous solution 6.5111, itaconic acid 2.3
g, dimethylaminoethyl methacrylate 11.3 (J
After charging 2.1 g of α-methylstyrene and adjusting the pH to 4.0 with a 15% aqueous sulfuric acid solution, nitrogen gas was introduced to remove oxygen from the reaction system.
次いで５５℃に昇温し、触媒として過硫酸アンモニウム
０．２４Ｑ及び亜硫酸ナトリウム０．０８ｇを投入し、
重合を開始した０反応により発熱して９１℃まで昇温し
て、発熱は停止した。Next, the temperature was raised to 55°C, and 0.24Q of ammonium persulfate and 0.08g of sodium sulfite were added as catalysts.
Due to the zero reaction that started polymerization, heat was generated and the temperature was raised to 91° C., and then the heat generation stopped.
５分後に過硫酸アンモニウム０．０４ｇを投入し、６０
分間８５℃以上に保温して、重合を停止させて共重合体
水浴液を得た。After 5 minutes, 0.04 g of ammonium persulfate was added and 60
The polymerization was stopped by keeping the temperature at 85° C. or higher for minutes to obtain a copolymer water bath solution.
実施例３〜２０
使用するモノマー成分を、表１に示すように変更し、実
施例１と同じ触媒を使用し、同様に操作して共重合体水
溶液を得た。Examples 3 to 20 The monomer components used were changed as shown in Table 1, the same catalyst as in Example 1 was used, and the same operation was performed to obtain an aqueous copolymer solution.
比較例１
実施例１において述べたと同じ四ツ目フラスコに、水２
７５Ｑ 、４０％アクリルアミド水溶液１４４、０ｇ、
６０％アクリル酸水溶液６．５ｇ及びジメチルアミンエ
チルメタクリレート５．７ｇを仕込み、１５％硫酸水溶
液でｐＨ４，０に調節した後、窒素ガスを導入して、反
応系中の酸素を除去した。Comparative Example 1 Into the same four-eye flask as described in Example 1, 2 liters of water was added.
75Q, 40% acrylamide aqueous solution 144, 0g,
After charging 6.5 g of 60% acrylic acid aqueous solution and 5.7 g of dimethylamine ethyl methacrylate and adjusting the pH to 4.0 with 15% sulfuric acid aqueous solution, nitrogen gas was introduced to remove oxygen in the reaction system.
次いで５５℃に昇温して、触媒として、イソプロピルア
ルコール０．５Ｑ、過硫酸アンモニウム０．１５９及び
亜硫酸ナトリウム０．０４＋Ｉｔを投入し、重合を開始
した０反応により発熱して９４℃まで昇温して発熱は停
止した後、６０分間８５℃以上に保温して、重合を停止
させて共重合体水溶液を得た。Next, the temperature was raised to 55°C, and 0.5Q of isopropyl alcohol, 0.159% of ammonium persulfate, and 0.04+It of sodium sulfite were added as catalysts, and the temperature was raised to 94°C with heat generated by the 0 reaction that started polymerization. After the heat generation stopped, the temperature was kept at 85° C. or higher for 60 minutes to stop the polymerization and obtain an aqueous copolymer solution.
比較例２
実施例１において述べたと同じ四ツ目フラスコに、水２
８０ｇ、４０％アクリルアミド水溶液１４９．１１．６
０％アクリル酸水溶液６．５Ｑ、イタコンｉ１２．３ｇ
及びジメチルアミンエチルメタクリレート１１．３ｇを
仕込み、１５％硫酸水溶液でｐＨ１４，０に調節した後
、窒素ガスを導入して、反応系中の酸素を除去した。Comparative Example 2 Into the same four-eye flask as described in Example 1, 2 liters of water was added.
80g, 40% acrylamide aqueous solution 149.11.6
0% acrylic acid aqueous solution 6.5Q, Itacon i 12.3g
After charging 11.3 g of dimethylamine ethyl methacrylate and adjusting the pH to 14.0 with a 15% aqueous sulfuric acid solution, nitrogen gas was introduced to remove oxygen from the reaction system.
次いで５５°Ｃに昇温して、触媒として、過硫酸アンモ
ニウム０．２４ｇ及び亜硫酸ナトリウム０゜０８ｇを投
入し、重合を開始した０反応により発熱して９４°Ｃま
で昇温して発熱は停止した後、６０分間８５°Ｃ以上に
保温して、重合を停止させて共重合体水溶液を得た。Next, the temperature was raised to 55°C, and 0.24g of ammonium persulfate and 0.08g of sodium sulfite were added as catalysts, and the reaction that started polymerization generated heat, and the temperature rose to 94°C, and the heat generation stopped. Thereafter, the temperature was kept at 85° C. or higher for 60 minutes to stop polymerization and obtain an aqueous copolymer solution.
比較例３〜１４
使用するモノマー成分を、表１に示すように変更し、比
較例２と同じ触媒を使用し、同様に操作して共重合体水
溶液を得た。なお比較例５及び８については、比較例１
と同じ触媒及び操作により行った。Comparative Examples 3 to 14 A copolymer aqueous solution was obtained by changing the monomer components used as shown in Table 1, using the same catalyst as in Comparative Example 2, and performing the same operation. Regarding Comparative Examples 5 and 8, Comparative Example 1
The same catalyst and procedure were used.
表１においては、各成分の量を、（ａ）〜（ｄ）の成分
の合計を１００とした、モル％により表示した。従って
（ｅ）成分については、その量に相当する分だけ合計量
が１００を越える。In Table 1, the amount of each component is expressed as mol%, with the total of components (a) to (d) being 100. Therefore, the total amount of component (e) exceeds 100 by the amount corresponding to that amount.
なお表１における各成分の物質は、次の略号により表示
している。The substances of each component in Table 1 are indicated by the following abbreviations.
（ａ）成分
ＡＭニアクリルアミド
（ｂ）成分
ＡＡニアクリル酸
ＩＡ：イタコン酸
ＭＡ：マレイン酸
（ｃ）成分
ＤＭニジメチルアミンエチルメタクリレートＤＭＢＣニ
ジメチルアミノエチルメタクリレートの塩化ベンジルに
よる四級化物
ＤＭＣニジメチルアミノエチルメタクリレートの塩化メ
チルによる四級化物
（ｄ）成分
ＳＴ：スチレン
αＭＳＴ：α−メチルスチレン
ｎ−ＢｔＡ：ｎ−ブチルアクリレート
−Ｂｔ、Ａ：インブチルアクリレート
（ｅ）成分
ＭＢＡＭ ：メチレンビスアクリルアミド得られた共重
合体水溶液について、固形分、粘度及び分子量を測定し
た。(a) Component AM Niacrylamide (b) Component AA Niacrylic Acid IA: Itaconic Acid MA: Maleic Acid (c) Component DM Nidimethylamine Ethyl Methacrylate DMBC Quaternization product of Nidimethylaminoethyl methacrylate with benzyl chloride DMC Nidimethylaminoethyl Quaternization of methacrylate with methyl chloride (d) Component ST: Styrene αMST: α-methylstyrene n-BtA: n-butyl acrylate-Bt, A: Inbutyl acrylate (e) Component MBAM: Methylenebisacrylamide The solid content, viscosity, and molecular weight of the aqueous polymer solution were measured.
固形分は、水溶液を乾燥させて、その不揮発分として測
定した。The solid content was determined by drying the aqueous solution and measuring its nonvolatile content.
粘度は、２５℃におけるプルツク・フィールド粘度によ
った。The viscosity was determined by Pruck-field viscosity at 25°C.
分子量は、東ソー株式会社製低角度光散乱度計ＬＳ−８
及びカラムＴｙｐｅ ＰＷＸＬを使用し、ポリエチレ
ンオキサイド標準サンプル（ＳＥ−１５０）を基準とし
て、各重合物の分子量を決定した。The molecular weight was measured using a low-angle light scattering meter LS-8 manufactured by Tosoh Corporation.
Using a column Type PWXL, the molecular weight of each polymer was determined based on a polyethylene oxide standard sample (SE-150).
各共重合体についての測定値は、表１の特性の欄に示す
通りであった。The measured values for each copolymer were as shown in the properties column of Table 1.
製紙用添加剤としての試験
段ボール古紙から得られたカナデイアン・スタンダード
・フリーネス（Ｃ，Ｓ、Ｆ、）４３０ｍｌに、硫酸バン
ドを２．０％添加し、ｐＨ５，５となるように調節した
。Test as an additive for papermaking To 430 ml of Canadian Standard Freeness (C, S, F,) obtained from waste corrugated paper, 2.0% of sulfuric acid was added and the pH was adjusted to 5.5.
次いで、紙力剤として、上記実施例及び比較例で得られ
た各重合体水溶液の主なものについて、当該水溶液を、
対バルブ０．３．０．６及び０゜９％添加した。撹拌し
た後パルプスラリー濃度を０．１％となるように稀釈し
て、手抄き装置で抄紙しな。Next, as a paper strength agent, the main aqueous solutions of each of the polymer aqueous solutions obtained in the above Examples and Comparative Examples were used.
Added 0.3, 0.6 and 0°9% to valve. After stirring, dilute the pulp slurry to a concentration of 0.1% and make paper using a hand paper machine.
抄紙後５ｋｇで２分間プレスし、次いでドラムドライヤ
ーで１０５°Ｃにおいて３分間乾燥し、２０°Ｃ１６５
％ＲＨの条件下で２４時間調湿した後、ＪＩＳ Ｐ−８
１１２及びＪＩＳ Ｐ−８１２６に準じて、比破裂強さ
及び比圧縮強さを測定した。After paper making, it was pressed for 2 minutes at 5 kg, then dried for 3 minutes at 105°C in a drum dryer, and then dried at 20°C at 165°C.
After conditioning the humidity for 24 hours under the condition of %RH, JIS P-8
112 and JIS P-8126, the specific bursting strength and specific compressive strength were measured.
結果を表２に示す。The results are shown in Table 2.
発明の効果
本発明によれば、表１からも明らかな如く、（ｄ）成分
を追加することにより、共重合体水溶液の粘度が大巾に
低下する。この点は実施例１と比較例１とを対比すると
明白である。すなわち実施例１は、比較例１に対して、
（ａ）成分のアクリルアミドの一部を、（ｄ）成分のス
チレンに置換えたものである。そしてその特性は、分子
量ははゾ同レベルであるにも拘らず、粘度は一部低い値
を示している。Effects of the Invention According to the present invention, as is clear from Table 1, by adding component (d), the viscosity of the aqueous copolymer solution is significantly reduced. This point becomes clear when comparing Example 1 and Comparative Example 1. That is, in Example 1, compared to Comparative Example 1,
A part of the acrylamide in the component (a) is replaced with the styrene in the component (d). Their characteristics include that although their molecular weights are on the same level, their viscosity is partially lower.
粘度のみを適正範囲に設定するのであれば、触媒を変更
することにより可能であるが、分子量が低下する。比較
例２は触媒を変更して重合度を調節し、粘度が過度に高
くなるのを防止したものであるが、このものにおいては
粘度は適正な範囲内であるものの、分子量が低く、共重
合体としての性能が劣る。Setting only the viscosity within an appropriate range can be done by changing the catalyst, but this will reduce the molecular weight. In Comparative Example 2, the degree of polymerization was adjusted by changing the catalyst to prevent the viscosity from becoming excessively high. Although the viscosity was within an appropriate range, the molecular weight was low and the copolymerization Performance as a combination is poor.
さらに比較例２に（ｄ）成分を追加すると、実施例２に
示されるように、粘度は大巾に低下している。Further, when component (d) was added to Comparative Example 2, the viscosity was significantly reduced as shown in Example 2.
（ａ）、（ｂ）、（ｃ）の各成分を変更して実施例３〜
２０の共重合体水溶液を合成したが、いずれも分子量が
大きく且つ粘度が適正なものであった。Example 3~ by changing each component of (a), (b), and (c)
20 copolymer aqueous solutions were synthesized, all of which had large molecular weights and appropriate viscosities.
比較例３〜１４においては、触媒により粘度を適性範囲
に設定しているが、いずれも分子量が低いものとなって
いる。比較例５．８に示すように分子量を大きくすると
、粘度が極めて高いものとなっている。In Comparative Examples 3 to 14, the viscosity was set within an appropriate range using a catalyst, but the molecular weights were all low. As shown in Comparative Example 5.8, when the molecular weight is increased, the viscosity becomes extremely high.
このように、本発明における（ｄ）成分により、共重合
体水溶液の粘度が低くなり、また同じ粘度範囲において
は重合度を高めることが可能であり、使用し易いものと
なる。As described above, component (d) in the present invention lowers the viscosity of the aqueous copolymer solution, and also makes it possible to increase the degree of polymerization within the same viscosity range, making it easy to use.
またこれらの水溶性ポリマーを製紙用添加剤として使用
した場合には、紙の耐水性が向上し、高湿度の環境下に
おいても、高い圧縮強度と層間接着強度が付与される。Furthermore, when these water-soluble polymers are used as papermaking additives, the water resistance of the paper is improved, and high compressive strength and interlayer adhesive strength are imparted even in a high humidity environment.
Claims (1)
７０〜９８．５モル％と、（ｂ）前記（ａ）成分と共重
合可能な水溶性アニオン性モノマー及び／又はその塩を
１〜２０モル％及び／又は、（ｃ）前記（ａ）成分と共
重合可能な水溶性カチオン性モノマー及び／又はその塩
を１〜２０モル％と、（ｄ）前記（ａ）成分と共重合可
能な疎水性モノマー及び／又はその塩を０．５〜１０モ
ル％とを共重合してなることを特徴とする、水溶性ポリ
マー ２ 前記（ｄ）成分が、 一般構造式 ▲数式、化学式、表等があります▼（１） （Ｒ＿１、Ｒ＿２：水素又は低級アルキル基）で示され
るスチレン誘導体であることを特徴とする、請求項１に
記載の水溶性ポリマー ３ 架橋剤を０．０１〜２モル％使用して共重合したこ
とを特徴とする、請求項１に記載の水溶性ポリマー ４ 請求項１〜３のいずれかに記載の水溶性ポリマーの
水溶液を主成分とすることを特徴とする、製紙用添加剤[Scope of Claims] 1 (a) 70 to 98.5 mol% of acrylamide and/or methacrylamide; (b) a water-soluble anionic monomer copolymerizable with component (a) and/or a salt thereof; 1 to 20 mol% and/or (c) 1 to 20 mol% of a water-soluble cationic monomer and/or its salt copolymerizable with the component (a), and (d) copolymerizable with the component (a). Water-soluble polymer 2, characterized in that it is formed by copolymerizing 0.5 to 10 mol% of a polymerizable hydrophobic monomer and/or a salt thereof.The component (d) has the general structural formula▲mathematical formula, chemical formula , tables, etc. ▼ (1) Water-soluble polymer 3 according to claim 1, characterized in that it is a styrene derivative represented by (R_1, R_2: hydrogen or lower alkyl group). The water-soluble polymer 4 according to claim 1, characterized in that it is copolymerized using 2 mol%.The water-soluble polymer 4 according to claim 1, characterized in that the main component is an aqueous solution of the water-soluble polymer according to any one of claims 1 to 3. Additive for paper making
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15824090A JPH0446915A (en) | 1990-06-15 | 1990-06-15 | Water-soluble polymer and paper-making additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15824090A JPH0446915A (en) | 1990-06-15 | 1990-06-15 | Water-soluble polymer and paper-making additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0446915A true JPH0446915A (en) | 1992-02-17 |
Family
ID=15667330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15824090A Pending JPH0446915A (en) | 1990-06-15 | 1990-06-15 | Water-soluble polymer and paper-making additive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0446915A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002077048A3 (en) * | 2001-03-22 | 2003-04-24 | Kimberly Clark Co | Ion-sensitive cationic polymers and fibrous items using same |
| WO2004027146A1 (en) * | 2002-09-20 | 2004-04-01 | Kimberly-Clark Worldwide, Inc. | A method of making a wet wipe |
| WO2004026926A1 (en) * | 2002-09-20 | 2004-04-01 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
| JP2020176336A (en) * | 2019-04-16 | 2020-10-29 | ハイモ株式会社 | Paper strength enhancing agent |
-
1990
- 1990-06-15 JP JP15824090A patent/JPH0446915A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002077048A3 (en) * | 2001-03-22 | 2003-04-24 | Kimberly Clark Co | Ion-sensitive cationic polymers and fibrous items using same |
| KR100849259B1 (en) * | 2001-03-22 | 2008-07-29 | 킴벌리-클라크 월드와이드, 인크. | Water?dispersible, cationic polymers, a method of making same and items using same |
| WO2004027146A1 (en) * | 2002-09-20 | 2004-04-01 | Kimberly-Clark Worldwide, Inc. | A method of making a wet wipe |
| WO2004026926A1 (en) * | 2002-09-20 | 2004-04-01 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
| US6960371B2 (en) * | 2002-09-20 | 2005-11-01 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
| JP2020176336A (en) * | 2019-04-16 | 2020-10-29 | ハイモ株式会社 | Paper strength enhancing agent |
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