JPH0316363B2 - - Google Patents
Info
- Publication number
- JPH0316363B2 JPH0316363B2 JP55095790A JP9579080A JPH0316363B2 JP H0316363 B2 JPH0316363 B2 JP H0316363B2 JP 55095790 A JP55095790 A JP 55095790A JP 9579080 A JP9579080 A JP 9579080A JP H0316363 B2 JPH0316363 B2 JP H0316363B2
- Authority
- JP
- Japan
- Prior art keywords
- dione
- polymerization
- metone
- solution
- acrylamide
- 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.)
- Expired - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 54
- SURCGQGDUADKBL-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-5-nitrobenzo[de]isoquinoline-1,3-dione Chemical group [O-][N+](=O)C1=CC(C(N(NCCO)C2=O)=O)=C3C2=CC=CC3=C1 SURCGQGDUADKBL-UHFFFAOYSA-N 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 12
- 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 claims description 10
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- -1 cyclic organic compound Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical group CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 claims description 3
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 19
- 239000004202 carbamide Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical compound C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical class CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical class CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- FDRMJKDXTZDBHQ-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;methyl hydrogen sulfate Chemical compound COS([O-])(=O)=O.C[NH+](C)CCOC(=O)C(C)=C FDRMJKDXTZDBHQ-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical class CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- LPRKNOCNWLAZRA-UHFFFAOYSA-N 2-[(1-carboxy-1-cyanobutyl)diazenyl]-2-cyanopentanoic acid Chemical compound CCCC(C(O)=O)(C#N)N=NC(C(O)=O)(C#N)CCC LPRKNOCNWLAZRA-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- CZYYPRGCWXYIPM-UHFFFAOYSA-N 4a,5,6,7-tetrahydro-4h-naphthalene-1,3-dione Chemical compound C1CCC=C2C(=O)CC(=O)CC21 CZYYPRGCWXYIPM-UHFFFAOYSA-N 0.000 description 1
- VUUNCMULTZRHHS-UHFFFAOYSA-N 5,5-diethylcyclohexane-1,3-dione Chemical compound CCC1(CC)CC(=O)CC(=O)C1 VUUNCMULTZRHHS-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000006434 Ritter amidation reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- VHSPRUFVQLFKKA-UHFFFAOYSA-N [Cl-].CC=CC(=O)NCCC[N+](C)(C)C Chemical compound [Cl-].CC=CC(=O)NCCC[N+](C)(C)C VHSPRUFVQLFKKA-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UIFJOXOHICDFDO-UHFFFAOYSA-N benzene-1,3,5-triol Chemical compound OC1=CC(O)=CC(O)=C1.OC1=CC(O)=CC(O)=C1 UIFJOXOHICDFDO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000402 conductometric titration Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VIDCUPKHAMMBHZ-UHFFFAOYSA-N cyclodecane-1,3-dione Chemical compound O=C1CCCCCCCC(=O)C1 VIDCUPKHAMMBHZ-UHFFFAOYSA-N 0.000 description 1
- DBOVMTXPZWVYAQ-UHFFFAOYSA-N cycloheptane-1,3-dione Chemical compound O=C1CCCCC(=O)C1 DBOVMTXPZWVYAQ-UHFFFAOYSA-N 0.000 description 1
- XZDMGEBEHZDGES-UHFFFAOYSA-N cyclooctane-1,2-dione Chemical compound O=C1CCCCCCC1=O XZDMGEBEHZDGES-UHFFFAOYSA-N 0.000 description 1
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical class CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Chemical class CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical class CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、水溶性の高分子量合成重合体、及び
特に単量体が不純物を許容できない程高量で含有
するために、例えば過度な量の不溶物及び/又は
許容できない程の低粘度及び/又は重合の低速度
を有して貧弱な重合体を生成する場合に、該水溶
性の高分子量合成重合体を製造する方法に関す
る。
更に詳細には、本発明は残基
を含有する環式化合物を用いることにより、特に
純粋な単量体から製造される重合体と本質的に同
一であるアクリルアミド及び/又はアクリル酸及
び/又は2−アクリルアミド−2−メチル−プロ
パンスルホン酸及びその塩の重合体を製造するこ
とに関する。
アクリルアミドは技術的に十分公知のアクリロ
ニトリルの水和によつて通常製造されている。こ
の物質は、一般に濃(40〜60重量%)溶液として
反応器に存在する。アクリル酸は通常技術的に十
分公知のプロピレンの酸化によつて通常製造され
ている。この物質は一般に濃溶液、即ち60%〜氷
アクリル酸として供給される。2−アクリルアミ
ド−2−メチルプロパンスルホン酸は、通常リツ
ター反応によりアクリロニトリル及び硫酸から製
造される。この物質はしばしば再結晶によつて精
製しなければならない固体粉末である。経済的な
理由のために、これらの生成物は水溶性の高分子
量生成物に直接せしめることが必要である。しか
しながら、これらの単量体溶液又は粉末は、今日
まで正確な量と種類が決定されていないが、明ら
かにppmの程度で未知の不純物を含有している。
このような単量体を重合させる場合、非常に低量
の不純物であつたとしても、全くしばしば全体的
に許容されない重合体が生成する。
液液重合において、これらの問題を解決する試
みは、(a)非常に低い乾燥温度;(b)単量体溶液の過
度な及び費用のかかる精製;(c)非常に長い重合時
間;(d)非常に多量の尿素の単量体への添加;及
び/又は(e)非常に薄い溶液での重合、を必要とし
た。しかしこれらの各々は、大規模な工業の場合
重合体の生成速度が著るしく減少し或いは望まし
い重合体の含量が許容できない程度まで低下する
ということに基づいて、エネルギーが多量に必要
であり又は費用がかかるが故に満足されはしなか
つた。
油中水性乳化重合において、これらの問題を解
決する試みは、(a)単量体の精製;(b)非常に希釈な
溶液の重合;(c)異なる開始剤の使用;(d)尿素の単
量体への添加;及び(e)連鎖移動剤の使用、を含ん
だ。しかしながら、これらも上述と同一の又は同
様の理由のために満足されなかつた。
従つて本発明の目的は、これらの問題を克服し
及び費用のかかる精製、即ち結晶化を行なわずに
濃単量体溶液を重合せしめることである。
本発明の更なる目的は、溶液重合した乾燥ポリ
アクリルアミド及びポリアクリル酸重合体中の不
溶物含量を商業的に許容しうる量、即ち約2重量
%以下に減ずることである。
本発明の更なる目的は、乳化重合したポリアク
リルアミド及びポリアクリル酸重合体の標準的な
粘度を許容しうる程度、即ちそれぞれ約4.5セン
チポイズ及び5.0センチポイズ以上まで増加させ
ることである。
本発明の更なる目的は、アクリルアミド又はア
クリル酸又は2−アクリルアミド−2−メチルプ
ロパンスルホン酸重合体の重合中及び/又は乾燥
もしくはミル処理中に生成する架橋重合体の量を
減少させることである。
本発明の更なる目的は、アクリル酸及び2−ア
クリルアミド−2−メチルプロパンスルホン酸型
単量体の重合速度を増加させることである。
本発明によると、式
の残基を含有する環式有機化合物を有するアクリ
ルアミド及び/又はアクリル酸及び/又は2−ア
クリルアミド−2−メチルプロパンスルホン酸の
単量体溶液が与えられる。好ましくは、環式化合
物(以下1,3−ジオンとして言及)は、単量体
の重合反応後に改良された生成物、好ましくは商
業的に許容しうる生成物を生成し及び/又は重合
速度を増加させるような十分な量で存在する。溶
液重合の場合、これは一般に約2重量%以下の不
溶物含量を意味する。アクリルアミド又はアクリ
ル酸の単独乳化重合の場合、これは標準粘度を故
意に約4.5センチポイズ以下に減少させない程十
分低い不溶物含量を意味する。それより低粘度の
乳化重合生成物が望ましい場合には、1,3−ジ
オンを用いて反応速度を増加させることができ
る。アクリル酸又は2−アクリルアミド−2−メ
チルプロパンスルホン酸及びその塩の単独重合の
場合、これは重合速度の増加を意味する。
本発明によれば、アクリルアミド又はアクリル
酸単量体を、随時他のエチレン性不飽和単量体と
共に水溶液中で重合させ、及び得られた重合体を
乾燥し、但し少くともこの乾燥を1,3−ジオン
の存在下に行なうことを含んでなる、不溶物含量
が約2%以下に減ぜられた水溶性の高分子量ポリ
アクリルアミド又はポリアクリル酸を製造する方
法が与えられる。
更に、アクリルアミド又はアクリル酸又は2−
アクリルアミド−2−メチルプロパンスルホン酸
単量体を、随時他のエチレン性不飽和の単量体と
共に、1,3−ジオンを存在させて乳化重合させ
ることを含んでなる水溶性の高分子量重合体を製
造する方法が与えられる。
更に2−アクリルアミド−2−メチルプロパン
スルホン酸及びその塩の単独重合体の重合反応を
1,3−ジオンの存在下に行なう該反応速度を増
加させる方法が与えられる。
これらの及び他の目的は、以下の詳細な記述か
ら容易に明らかとなるであろう。
改良された重合体を製造するために本発明で使
用される化合物は、式
の残基を含有する環式有機化合物である。これら
の化合物は、残基が化合物中の他の位置に存在し
てもよいけれど、1,3−ジオンとして言及され
る。
そのような1,3−ジオンの例は、1,3−シ
クロペンタンジオン;1,3−シクロヘキサンジ
オン;1,3−シクロヘプタンジオン;1,3−
シクロオクタンジオン;1,3−シクロデカンジ
オン;5,5−ジメチル−1,3−シクロヘキサ
ンジオン;5,5−ジエチル−1,3−シクロヘ
キサンジオン;1,3,5−シクロヘキサントリ
オン及びその互変異性体フロログルシノール
(1,3,5−トリヒドロキシベンゼン);テトラ
ヒドロナフタレン−1,3−ジオン;バルビツル
酸;及び他のそのような化合物の置換された及び
置換されていない誘導体を含むが、これらに限定
されるものではない。
基
The present invention is directed to water-soluble high molecular weight synthetic polymers, and especially monomers, which contain unacceptably high amounts of impurities, such as excessive amounts of insolubles and/or unacceptably low viscosity and/or polymerization. The present invention relates to a method for producing water-soluble, high molecular weight synthetic polymers in which the present invention has a low rate of oxidation to produce a poor polymer. More specifically, the present invention provides residues In particular, by using cyclic compounds containing acrylamide and/or acrylic acid and/or 2-acrylamido-2-methyl-propanesulfonic acid which are essentially identical to the polymers prepared from pure monomers. and to producing polymers of salts thereof. Acrylamide is commonly prepared by hydration of acrylonitrile, which is well known in the art. This material is generally present in the reactor as a concentrated (40-60% by weight) solution. Acrylic acid is commonly produced by the oxidation of propylene, which is well known in the art. This material is generally supplied as a concentrated solution, ie 60% to glacial acrylic acid. 2-Acrylamido-2-methylpropanesulfonic acid is usually produced from acrylonitrile and sulfuric acid by the Ritter reaction. This material is often a solid powder that must be purified by recrystallization. For economic reasons, it is necessary to convert these products directly into water-soluble high molecular weight products. However, these monomer solutions or powders contain unknown impurities, apparently in the ppm range, although the exact amounts and types have not been determined to date.
When such monomers are polymerized, even with very low amounts of impurities, totally unacceptable polymers are often formed. In liquid-liquid polymerization, attempts to solve these problems have resulted in (a) very low drying temperatures; (b) excessive and expensive purification of the monomer solution; (c) very long polymerization times; (d ) addition of very large amounts of urea to the monomers; and/or (e) polymerization in very dilute solutions. However, each of these requires high amounts of energy or They were not satisfied with it because it was expensive. Attempts to solve these problems in water-in-oil emulsion polymerization have focused on (a) monomer purification; (b) very dilute solution polymerization; (c) use of different initiators; (d) urea and (e) the use of chain transfer agents. However, these were also not satisfied for the same or similar reasons as mentioned above. The object of the present invention is therefore to overcome these problems and to polymerize concentrated monomer solutions without expensive purification, ie crystallization. A further object of the present invention is to reduce the insoluble content in solution polymerized dry polyacrylamide and polyacrylic acid polymers to commercially acceptable amounts, ie, less than about 2% by weight. A further object of the present invention is to increase the standard viscosity of emulsion polymerized polyacrylamide and polyacrylic acid polymers to an acceptable degree, ie, to above about 4.5 centipoise and 5.0 centipoise, respectively. A further object of the present invention is to reduce the amount of crosslinked polymer formed during the polymerization and/or during drying or milling of acrylamide or acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid polymers. . A further object of the present invention is to increase the rate of polymerization of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid type monomers. According to the invention, the formula A monomer solution of acrylamide and/or acrylic acid and/or 2-acrylamido-2-methylpropanesulfonic acid with a cyclic organic compound containing the residue of is provided. Preferably, the cyclic compound (hereinafter referred to as 1,3-dione) produces an improved product, preferably a commercially acceptable product, after the polymerization reaction of the monomers and/or increases the rate of polymerization. present in sufficient quantity to increase In the case of solution polymerization, this generally means an insolubles content of about 2% by weight or less. In the case of homoemulsion polymerization of acrylamide or acrylic acid, this means an insoluble content low enough that the standard viscosity is not intentionally reduced below about 4.5 centipoise. If a lower viscosity emulsion polymerization product is desired, 1,3-diones can be used to increase the reaction rate. In the case of homopolymerization of acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid and its salts, this means an increase in the polymerization rate. According to the invention, the acrylamide or acrylic acid monomer is polymerized in an aqueous solution, optionally together with other ethylenically unsaturated monomers, and the resulting polymer is dried, provided that at least this drying is A method of making a water-soluble high molecular weight polyacrylamide or polyacrylic acid having a reduced insoluble content of about 2% or less is provided, the method comprising carrying out the process in the presence of a 3-dione. Furthermore, acrylamide or acrylic acid or 2-
A water-soluble high molecular weight polymer comprising emulsion polymerization of acrylamide-2-methylpropanesulfonic acid monomer, optionally with other ethylenically unsaturated monomers, in the presence of 1,3-dione. A method of manufacturing is provided. Furthermore, a method is provided for increasing the reaction rate of a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid and its salts in the presence of 1,3-dione. These and other objects will become readily apparent from the detailed description below. The compounds used in this invention to make improved polymers have the formula is a cyclic organic compound containing the residue of These compounds are referred to as 1,3-diones, although the residue may be present in other positions within the compound. Examples of such 1,3-diones are 1,3-cyclopentanedione; 1,3-cyclohexanedione; 1,3-cycloheptanedione;
Cyclooctanedione; 1,3-cyclodecanedione; 5,5-dimethyl-1,3-cyclohexanedione; 5,5-diethyl-1,3-cyclohexanedione; 1,3,5-cyclohexantrone and its tautomer phloroglucinol (1,3,5-trihydroxybenzene); tetrahydronaphthalene-1,3-dione; barbituric acid; and substituted and unsubstituted derivatives of other such compounds. It is not limited to these. base
【式】を有する上記化合物の互変
異性体も、本発明で使用される1,3−ジオンの
意味に包含される。これには、カルバルコキシジ
メドン金属エノレート、例えばカルボメトキシジ
メドンナトリウムエノレート、カルボエトキシジ
メドンカリウムエノレートなどを含む金属エノレ
ートがある。
最も好ましくは、1,3−ジオンは、メトン又
はジメトンとしても公知である5,5−ジメチル
−1,3−シクロヘキサンジオンである。
1,3−ジオンを単量体に添加し及び次いで単
量体を重合させる場合、1,3−ジオンは重合禁
止剤であつてはならない。それが禁止剤であるな
らば、それを重合に先立つて単量体から除去しな
ければならない。そのような除去方法の一つは、
単量体溶液を活性炭床中に通過させることであ
る。他に溶液重合の場合、1,3−ジオンを乾燥
に先立つ重合体ゲルに添加してもよい。
更に1,3−ジオンが重合条件下に安定でない
場合には、不安定化を避けるために重合条件を変
えねばならず、或いは1,3−ジオンを乾燥に先
立つ重合体ゲルに添加しなければならない。
以下に詳細に述べるいくつかの場合、約20重量
%(単量体含量に基づく)の尿素又は尿素誘導体
を1,3−ジオンと共に含有させることが望まし
いことが発見された。好ましくは5〜10%の尿素
それ自体が使用される。適当なそのような化合物
は、本明細書に引用される米国特許第3622533号
に開示されている。尿素は1,3−ジオンの前
に、後に又は同時に添加することができる。
本発明で重合せしめうる単量体は、アクリルア
ミド、アクリル酸、及び2−アクリルアミド−2
−メチルプロパンスルホン酸及びその塩である。
これらの上述の単量体或いは単量体1種又はそれ
以上と水溶性生成物を製造するのに適当な他のエ
チレン性不飽和単量体との共重合体も製造するこ
とができる。そのような他の単量体は、メタクリ
ルアミド、アクリル酸の塩、メタクリル酸及びそ
の塩、アクリル酸メチル、アクリル酸エチル、ア
クリル酸プロピル、メタクリル酸メチル、メタク
リル酸エチル、アクリル酸ジメチルアミノエチ
ル、メタクリル酸ジメチルアミノエチル、アクリ
ル酸ジエチルアミノエチル、メタクリル酸ジエチ
ルアミノエチル、アクリル酸ヒドロキシエチル、
メタクリル酸ヒドロキシエチル、アクリル酸ジエ
チルアミノエチルメチルサルフエート、スチレ
ン、アクリロニトリル、3−(メチルアクリルア
ミド)プロピル−トリメチルアンモニウムクロラ
イド、ビニルメチルエーテル、ビニルエチルエー
テル、ビニルスルホン酸のアルカリ金属又はアン
モニウム塩、などを含むが、これらに限定される
ものではない。重合体のアクリルアミド部分のす
べて又は一部は加水分解されていてもよい。
本発明で使用しうる重合法は、そのような単量
体の重合に通常使用されるもののいずれであつて
もよい。これは特に溶液及び乳化重合を含むが、
他の技術例えばビーズ及び懸濁分散重合も使用で
きる。これらの各々の特別な重合系は通常使用さ
れるものである。溶液重合の場合、これは1種又
はそれ以上のアゾ開始剤をレドツクス系の有無下
に及び随時重合反応に必要な金属イオン封鎖剤
(sequesterants)、アルコール及び稀釈剤の有無
下に用いることを含む。油中水性乳化液の乳化重
合の場合、これは油中水性乳化剤、油相例えばト
ルエン、キシレン又はパラフイン油、及び遊離基
開始剤を用いることを伴なう。
本発明は用いる重合方法とは無関係であるの
で、それに関する更なる詳細は文献を参照された
い。更に量及び各々の成分は、重合される単量体
及び重合を行なう工程条件に従つて変化するであ
ろう。
本発明で用いる1,3−ジオンの量は、少くと
も部分的に重合方法の種類、単量体の精製の種
類、単量体/1,3−ジオン組成物の熟成の程
度、溶液重合の場合に生成物を製造し及び/又は
乾燥するときの温度、尿素の有無及びその量、濃
単量体溶液中の不純物の量、並びに重合体の最高
温度での滞留時間に依存することがわかつた。そ
ようなために、正確な“重合体を改良する量”を
定義することはできない。しかしながら、一般に
それは単量体に基づいて約0.001〜2重量%(又
はそれ以上)の範囲であり、更に特に乳化重合の
場合にはそれより多量、及び溶液重合の場合には
それより少量であつてもよい。乳化重合の場合、
熟成してない又は室温で熟成した溶液に対する好
適な量は約0.3〜1%、最も好適には約0.4〜0.7重
量%である。加速式(約50℃以上で約2時間以
上)の熟成を用いれば、好適な量は約0.005〜0.2
%、最も好ましくは0.007〜0.1%である。溶液重
合の場合、好適な量は約0.03〜0.4%及び最も好
適には約0.05〜0.25重量%である。
アクリルアミド及びアクリル酸の溶液重合に対
しては、(a)濃単量体溶液をカチオン交換樹脂及
び/又は活性炭と接触させて精製し;(b)乾燥温度
が約80℃以上、特に約85℃以上、更に特に90℃又
はそれ以上である場合に、尿素を更に使用し;及
び(c)できるだけ迅速に、即ち過度の熟成なしに、
単量体/1,3−ジオン溶液を用いることが有利
であると判明した。なお(a)において除去されるも
のは何であるか未知であるが、(a)の工程により改
良された結果が得られることもわかつた。更に本
発明の利点は、単量体に対してではなく、むしろ
乾燥前の得られる重合体ゲルに対して1,3−ジ
オンを添加することによつても具現化することが
できる。これは1,3−ジオンをゲル中へ均一に
混入することが非常に難しいという点で望ましい
とはいえない。しかしながら、これは1,3−ジ
オンが効果的であり、溶液重合の乾燥段階で働い
ていることを示している。
乳化重合に対しては、(a)使用前に約5日間単量
体/1,3−ジオン組成物を熟成させ、或いは(b)
使用前に数時間高温で(約5時間60〜80℃で)組
成物を熟成させる、ことが有利であると判明し
た。この熟成は1,3−ジオンの効果を高めるこ
とがわかつた。しかしながら、有利な効果は、多
量の1,3−ジオン、即ち単量体に基づいて約
0.9〜2%の1,3−ジオンを用いることにより、
熟成なしに具現化できた。
本発明のアクリルアミド又はアクリル酸/1,
3−ジオン溶液を調製するためには、重合に際し
て希釈する前に1,3−ジオンを単量体の濃溶液
に溶解することが有利であると判明した。これ
は、本質的に性能上の差が認められないけれど、
1,3−ジオンを希溶液へ溶解するために必要と
されることがわかつた時間の増大に起因してい
る。2−アクリルアミド−2−メチルプロパンス
ルホン酸/1,3−ジオン溶液を製造するために
は、2つの化合物を単に水と混合すればよい。
他に、1,3−ジオンは単量体を製造したアク
リロニトリル又はプロピレン中に導入してもよ
い。
次の実施例は、本発明のある観点を例示し、更
に特に本発明によつて得られる利点を指摘する。
しかしながら、実施例は単なる例示であり、特許
請求の範囲に示される如きものを除いて本発明を
限定するものではない。すべての部及びパーセン
トは断らない限り重量によるものとする。
実施例 1
アクリルアミド/1,3−ジオン溶液の製造
(a) ポリエチレンでライニングした容器に、好ま
しくは溶液重合の場合に続く重合反応も行なう
容器に、“入手状態”の51.3%水性アクリルア
ミド810.9g及びメトン0.83gを添加した。こ
の物質を空気中で約5分間磁気的に撹拌してメ
トンを溶解した。これはアクリルアミド単量体
に基づいて0.2%のメトンを含有した。
(b) メトンの添加に先立つて水性アクリルアミド
をカチオン交換樹脂〔ローム・アンド・ハース
社(Rohm and Hass)のAmberlite
IR−
120〕床中に通過させること以外(a)の工程を繰
返した。
(c) メトンの添加に先立つて水性アクリルアミド
を、(i)カチオン交換樹脂(Amberlite
IR−
120)床に通過させ、及び次いで(ii)活性炭
(Nuchar WV−L 8×30メツシユ)床中に
通過させる以外(a)の工程を繰返した。
(d) 他のそのような溶液を、下記実施例に示す如
き種々の量のメトンを用いて製造した。
実施例 2
実施例1(c)の単量体の溶液重合
実施例1(c)の単量体溶液を次の如く溶液重合し
た。それを1ガロンのポリエチレン反応器中に入
れ、磁気的に撹拌した。続いて撹拌しながら次の
ものを添加した:
脱イオン水 2311.2g
2%水性エチレンジアミン四酢酸 4.2ml
10%水性イソプロパノール 3.2ml
水性硫酸ナトリウム 16.6g
水性硫酸アンモニウム 4.2g
尿 素 20.8g
溶液が完全になつたとき、反応物体のPHを硫酸
で3.0に調節した。次いで反応物体を約35℃まで
暖めながら30分間窒素を約1000ml/時で流し始め
た。この窒素でのパージングを続けながら、触媒
2,2′−アゾビス(2,4−ジメチル−4−メ
トキシバレロニトリル)0.0078g/mlの13.3ml
2,2′−アゾビス(シアノ吉草酸)0.02g/ml
の15.6ml
を導入した。その後10分以内に重合が始まつた。
重合反応は、反応器を隔離することにより、実
質的に断熱的に継続させた。重合物は約2時間に
亘り29.8℃の発熱を経験した。その後、これを約
70℃で硬化炉に移し、そこで更に18時間硬化させ
ることにより硬いゲル生成物3200gを得た。
続いてこのゲルを細片に切断し、その一部分を
対流炉中において90、100及び113±2℃の温度下
に残存揮発物7〜10%まで乾燥した。乾燥した生
成物をウエアリング混合機(Waring Blender)
中で粒径を減じ、ふるいにかけて−20米国メツシ
ユの粒径の生成物を得た。
実施例 3
実施例2の生成物の評価
実施例2で製造した生成物を評価するために次
のことを行なつた:
各温度で乾燥した生成物0.3gを脱イオン水に
溶解して0.1%重合体水溶液300gを製造した。こ
の溶液を100米国メツシユの重量ふるいに通過さ
せて不溶物を分離した。次いでふるいを室温下に
脱イオン水約500mlで洗浄し、100℃で夜通し乾燥
し、次いで不溶物の量を決定して不溶物%として
報告した。
残存揮発物のパーセントは、1gの試料を100
〜110℃で2時間乾燥した後の重量損失を測定す
ることによつて決定した。
加水分解の程度(カルボキシル%)は重合体中
のカルボキシル含量を伝導度滴定によつて決定し
た。この場合数が低ければ低いほど、非イオン性
に対する得られる生成物は良好であつた。
“入手状態”の粘度は、生成物0.3gを脱イオ
ン水に2時間に亘つて溶解して300gの水溶液を
調製し、100米国メツシユふるいを通して不溶物
を分離し、次いで1モル濃度のNaCl溶液を調製
するのに十分な塩化ナトリウムを添加し、及び
ULアダプターを用いてブルツクフイールド粘度
を測定することによつて決定した。
これはその結果生じる生成物の性能を示し、数
が大きくなればなるほど最終生成物はより望まし
い。
結果を、メトンを使用しない以外同一の方法で
製造した比較例の結果と一緒に、下表に示す。
それらは、0.2%メトンを単量体に添加すること
により、“入手状態”の粘度が非常に増加し、及
び不溶物%が約60%から0.4以下%まで低下する
ということを明らかに示している。Tautomers of the above compounds having the formula are also included within the meaning of 1,3-dione as used in the present invention. These include metal enolates, including carbalkoxydimedone metal enolates, such as carbomethoxydimedone sodium enolate, carboethoxydimedone potassium enolate, and the like. Most preferably the 1,3-dione is 5,5-dimethyl-1,3-cyclohexanedione, also known as metone or dimetone. If the 1,3-dione is added to the monomer and the monomer is then polymerized, the 1,3-dione must not be a polymerization inhibitor. If it is an inhibitor, it must be removed from the monomer prior to polymerization. One such removal method is
The monomer solution is passed through a bed of activated carbon. Alternatively, in the case of solution polymerization, 1,3-dione may be added to the polymer gel prior to drying. Furthermore, if the 1,3-dione is not stable under the polymerization conditions, the polymerization conditions must be changed to avoid destabilization, or the 1,3-dione must be added to the polymer gel prior to drying. No. In some cases, detailed below, it has been found desirable to include about 20% by weight (based on monomer content) of urea or urea derivative with the 1,3-dione. Preferably 5-10% of urea itself is used. Suitable such compounds are disclosed in US Pat. No. 3,622,533, which is incorporated herein by reference. Urea can be added before, after or simultaneously with the 1,3-dione. Monomers that can be polymerized in the present invention include acrylamide, acrylic acid, and 2-acrylamide-2
-Methylpropanesulfonic acid and its salts.
Copolymers of these above-mentioned monomers or one or more monomers with other ethylenically unsaturated monomers suitable for producing water-soluble products can also be produced. Such other monomers include methacrylamide, salts of acrylic acid, methacrylic acid and its salts, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, dimethylaminoethyl acrylate, Dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, hydroxyethyl acrylate,
Contains hydroxyethyl methacrylate, diethylaminoethyl methyl acrylate sulfate, styrene, acrylonitrile, 3-(methylacrylamido)propyl-trimethylammonium chloride, vinyl methyl ether, vinyl ethyl ether, alkali metal or ammonium salts of vinyl sulfonic acid, etc. However, it is not limited to these. All or part of the acrylamide portion of the polymer may be hydrolyzed. Polymerization methods that can be used in the present invention can be any of those commonly used for polymerizing such monomers. This includes in particular solution and emulsion polymerizations, but
Other techniques such as bead and suspension dispersion polymerization can also be used. Each of these specific polymerization systems are those commonly used. In the case of solution polymerization, this involves the use of one or more azo initiators in the presence or absence of a redox system and optionally the presence or absence of sequesterants, alcohols and diluents necessary for the polymerization reaction. . In the case of emulsion polymerization of water-in-oil emulsions, this involves using a water-in-oil emulsifier, an oil phase such as toluene, xylene or paraffin oil, and a free radical initiator. Since the invention is independent of the polymerization method used, reference is made to the literature for further details thereon. Furthermore, the amounts and each component will vary according to the monomers being polymerized and the process conditions under which the polymerization is carried out. The amount of 1,3-dione used in the present invention depends, at least in part, on the type of polymerization method, the type of monomer purification, and the degree of ripening of the monomer/1,3-dione composition. It has been found that it depends on the temperature at which the product is prepared and/or dried in the case, the presence and amount of urea, the amount of impurities in the concentrated monomer solution, and the residence time of the polymer at the highest temperature. Ta. As such, it is not possible to define an exact "amount that improves the polymer." However, generally it will range from about 0.001 to 2% (or more) by weight based on monomer, and more particularly in the case of emulsion polymerization and less in the case of solution polymerization. It's okay. In the case of emulsion polymerization,
Preferred amounts for unaged or room temperature aged solutions are about 0.3-1%, most preferably about 0.4-0.7% by weight. If accelerated aging (approximately 2 hours or more at approximately 50°C or higher) is used, the suitable amount is approximately 0.005 to 0.2
%, most preferably 0.007-0.1%. For solution polymerization, suitable amounts are about 0.03-0.4% and most preferably about 0.05-0.25% by weight. For solution polymerization of acrylamide and acrylic acid, (a) the concentrated monomer solution is purified by contacting with a cation exchange resin and/or activated carbon; (b) the drying temperature is above about 80°C, especially about 85°C. (c) as quickly as possible, i.e. without undue ripening;
It has proven advantageous to use monomer/1,3-dione solutions. Although it is unknown what is removed in step (a), it has been found that improved results can be obtained by step (a). Moreover, the advantages of the invention can also be realized by adding 1,3-dione not to the monomers, but rather to the resulting polymer gel before drying. This is not desirable in that it is very difficult to uniformly mix 1,3-dione into the gel. However, this indicates that the 1,3-dione is effective and is working in the drying stage of the solution polymerization. For emulsion polymerization, (a) aging the monomer/1,3-dione composition for about 5 days before use; or (b)
It has proven advantageous to age the composition at elevated temperatures (approximately 5 hours at 60-80° C.) for several hours before use. This ripening was found to enhance the effectiveness of the 1,3-dione. However, the advantageous effect is that based on the large amount of 1,3-dione, i.e.
By using 0.9-2% 1,3-dione,
I was able to materialize it without any maturity. Acrylamide or acrylic acid of the present invention/1,
In order to prepare the 3-dione solution, it has proven advantageous to dissolve the 1,3-dione in a concentrated monomer solution before dilution during the polymerization. Although there is essentially no difference in performance,
This is due to the increased time found required to dissolve the 1,3-dione into dilute solution. To prepare the 2-acrylamido-2-methylpropanesulfonic acid/1,3-dione solution, the two compounds can simply be mixed with water. Alternatively, the 1,3-dione may be introduced into the acrylonitrile or propylene from which the monomer was prepared. The following examples illustrate certain aspects of the invention and more particularly point out the advantages obtained by the invention.
However, the examples are merely illustrative and do not limit the invention except as indicated in the claims. All parts and percentages are by weight unless otherwise noted. Example 1 Preparation of an acrylamide/1,3-dione solution (a) 810.9 g of 51.3% aqueous acrylamide "as received" and 0.83 g of metone was added. The material was stirred magnetically in air for approximately 5 minutes to dissolve the metone. It contained 0.2% metone based on acrylamide monomer. (b) Prior to the addition of metone, the aqueous acrylamide was treated with a cation exchange resin (Amberlite IR from Rohm and Hass).
120] Step (a) was repeated except passing through the bed. (c) Prior to the addition of metone, the aqueous acrylamide was treated with (i) a cation exchange resin (Amberlite IR-
120) and then (ii) repeated the process of (a) except passing through a bed of activated carbon (Nuchar WV-L 8x30 mesh). (d) Other such solutions were prepared using various amounts of metone as shown in the examples below. Example 2 Solution polymerization of the monomer of Example 1(c) The monomer solution of Example 1(c) was solution polymerized as follows. It was placed in a 1 gallon polyethylene reactor and stirred magnetically. The following were then added with stirring: 2311.2 g deionized water 4.2 ml 2% aqueous ethylenediaminetetraacetic acid 3.2 ml 10% aqueous isopropanol 16.6 g aqueous sodium sulfate 4.2 g aqueous ammonium sulfate 20.8 g urea until the solution was complete. At that time, the pH of the reaction mass was adjusted to 3.0 with sulfuric acid. Nitrogen flow was then started at about 1000 ml/hour for 30 minutes while the reaction mass was warmed to about 35°C. Continuing this purging with nitrogen, add 13.3 ml of catalyst 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) 0.0078 g/ml 2,2'-azobis(cyanovaleric acid) 0.02 g/ml ml
15.6ml of was introduced. Polymerization started within 10 minutes thereafter. The polymerization reaction was allowed to continue substantially adiabatically by isolating the reactor. The polymer experienced an exotherm of 29.8°C over approximately 2 hours. Then change this to approx.
Transferred to a curing oven at 70° C. and cured there for an additional 18 hours, yielding 3200 g of a hard gel product. The gel was then cut into strips and portions thereof were dried in a convection oven at temperatures of 90, 100 and 113±2° C. to a residual volatile content of 7-10%. Waring blender (Waring Blender)
The particle size was reduced in a vacuum and sieved to obtain a -20 US mesh particle size product. Example 3 Evaluation of the product of Example 2 To evaluate the product prepared in Example 2, the following was done: 0.3 g of the dried product at each temperature was dissolved in deionized water to give a concentration of 0.1 g. % polymer aqueous solution was prepared. The solution was passed through a 100 US mesh weight sieve to separate insoluble materials. The sieves were then washed with approximately 500 ml of deionized water at room temperature, dried overnight at 100°C, and the amount of insolubles was determined and reported as % insolubles. The percentage of residual volatiles is determined by measuring 1 g of sample to 100
Determined by measuring weight loss after drying at ~110°C for 2 hours. The degree of hydrolysis (% carboxyl) was determined by conductometric titration of carboxyl content in the polymer. In this case the lower the number, the better the product obtained for non-ionicity. The “as received” viscosity was determined by dissolving 0.3 g of the product in deionized water over 2 hours to make 300 g of an aqueous solution, passing it through a 100 US mesh sieve to separate insoluble material, and then passing it through a 100 US mesh sieve to separate the insolubles, then passing it through a 1 molar NaCl solution. add enough sodium chloride to prepare and
Determined by measuring Bruckfield viscosity using a UL adapter. This indicates the performance of the resulting product; the higher the number, the more desirable the final product. The results are shown in the table below along with the results of a comparative example produced in the same manner except without metone.
They clearly show that by adding 0.2% metone to the monomer, the "as-used" viscosity increases greatly and the % insolubles decreases from about 60% to less than 0.4%. There is.
【表】
実施例 4
メトンの量をそれぞれ0.10%及び0.05%に減ず
る以外実施例2及び3の方法を繰返した。
結果は次の通りであつた。Table: Example 4 The method of Examples 2 and 3 was repeated except that the amount of metone was reduced to 0.10% and 0.05%, respectively. The results were as follows.
【表】
それらは、メトンの量を減ずるにつれて不溶物
%が増加することを示している。またその量が
0.05%であり及び乾燥温度が100℃であるとき、
不溶物含量を2%以下にするのにはメトン量が不
十分であることがわかる。
実施例 5〜10
(1)精製法及び(2)メトン量、を変える以外実施例
2及び3の方法を繰返した。結果を表に示す。
表から明らかなように、メトン量が増加するにつ
れて、(“入手状態”の粘度の増加及び不溶物の減
少によつて示されるように)改良された生成物が
生成した。Table: They show that the % insolubles increases as the amount of metone is reduced. Also, the amount
When it is 0.05% and the drying temperature is 100℃,
It can be seen that the amount of metone is insufficient to reduce the insoluble matter content to 2% or less. Examples 5-10 The methods of Examples 2 and 3 were repeated except that (1) the purification method and (2) the amount of metone were changed. The results are shown in the table.
As can be seen from the table, as the amount of metone was increased, an improved product was produced (as shown by increased "as-sourced" viscosity and decreased insolubles).
【表】
実施例 11〜20
単量体の処理、尿素及びケトンの存在及び量、
触媒系及びPH、固定パーセント、最高温度、及び
最高温度での時間を表aに示すように変える以
外、実施例2及び3の基本的な工程を繰返した。
単量体の処置に関し、“YES”は実施例1bにおけ
る如くカチオン交換樹脂で処置したことを示し、
及び“NONE”は実施例1aにおける如く調製し
たことを示す。実施例2における(NH4)2SO4%
は1%、Na2SO4%は4%、及び尿素%は5%で
あつた。
乾燥生成物のデータを表bに示す。
1,3−ジオン及び/又は尿素を単量から省略
し且つゲルに添加して乾燥段階中だけ存在させう
るということを示すために、種々の後段添加を次
の如く行なつた:
実施例15−メトン0.1%及び尿素10%を後段添
加
実施例16−メトン0.1%だけを後段添加
実施例19及び20−尿素10%だけを後段添加
これらに対する乾燥生成物のデータも表bに
示す。
表a及びbのデータから理解できるよう
に、メトンの効果は触媒系又は重合条件に無関係
であり、メトン及び尿素の組合せ物を用いること
によつて利点が得られる。[Table] Examples 11-20 Treatment of monomers, presence and amount of urea and ketones,
The basic steps of Examples 2 and 3 were repeated, except that the catalyst system and PH, fixed percentage, maximum temperature, and time at maximum temperature were varied as shown in Table a.
For monomer treatment, "YES" indicates treatment with cation exchange resin as in Example 1b;
and "NONE" indicate prepared as in Example 1a. (NH 4 ) 2 SO 4 % in Example 2
was 1%, Na 2 SO 4 % was 4%, and urea % was 5%. The data for the dry product is shown in Table b. To demonstrate that the 1,3-dione and/or urea can be omitted from the monomers and added to the gel to be present only during the drying stage, various post-additions were made as follows: Example 15 - post-addition of 0.1% metone and 10% urea Example 16 - post-addition of only 0.1% metone Examples 19 and 20 - post-addition of only 10% urea The dry product data for these are also shown in Table b. As can be seen from the data in Tables a and b, the effect of metone is independent of catalyst system or polymerization conditions, and benefits are obtained by using a combination of metone and urea.
【表】【table】
【表】
実施例 21〜28
異なつた未処理の単量体、27%固体、金属イオ
ン封鎖剤としてのジエチレントリアミンペンタ酢
酸、触媒としての2,2′−アゾビス(2−アミジ
ノプロパン)塩酸塩且つ過硫酸アンモニウム/硫
酸第一鉄アンモニウムレドツクス系、PH6.0、0
℃での反応開始、及び滞留時間4時間、を用いる
以外実施例2及び3の基本的な工程を繰返した。
メトン及び尿素の使用量並びに約60〜70℃で揮
発物約12%まで乾燥した生成物に対する乾燥生成
物のデータを下表に示す。
これらの重合条件に基づいて理解されるよう
に、メトンだけで許容しうる生成物を生成し(即
ち入手状態の粘度が高く、及び不溶物が約2%以
下であり)、一方尿素だけではそのような生成物
を与えなかつた。[Table] Examples 21-28 Different untreated monomers, 27% solids, diethylenetriaminepentaacetic acid as sequestering agent, 2,2'-azobis(2-amidinopropane) hydrochloride and filtrate as catalyst. Ammonium sulfate/ferrous ammonium sulfate redox system, PH6.0, 0
The basic steps of Examples 2 and 3 were repeated except using a reaction initiation at 0.degree. C. and a residence time of 4 hours. Metone and urea usage and dry product data for products dried to about 12% volatiles at about 60-70°C are shown in the table below. As can be seen based on these polymerization conditions, metone alone produces an acceptable product (i.e., high as-available viscosity and less than about 2% insolubles), whereas urea alone produces It gave no such product.
【表】
実施例 29〜38
アクリルアミドの乳化重合
実施例1aにおける如き水性アクリルアミド溶
液に、メトンを約5分間撹拌しながら添加した。
次いでPHが9であるとき水酸化ナトリウムを添加
する以外次の工程を用いた。
適当な反応容器に、50.47%水溶液としてのア
クリルアミド2100.0部及び脱イオン水850.0部を
添加した。この溶液に、エチレンジアミン四酢酸
のジナトリウム塩2.12部及び水和硫酸第二鉄(72
%Fe2(SO4)3)1.15部を、H2O1000部当り4.5部と
して添加した。得られた溶液のPHを5.0に調節し
た。これは水性単量体相をなした。
油相は、ソルビタンモノオレエート90.0部を、
ユニオン・オイル・カンパニー・オブ・カリフオ
ルニア(Union Oil Co.of California)によつて
販売されている明るい油状液体AMSCO
OMS1040.0部に溶解することによつて製造した。
適当な高速ホモナイザーに、完全な油相系を添
加した。ホモナイザーを始動させ、これに単量体
水性相をゆつくり添加して粘度990cpsを有する乳
化液を生成させた。得られた乳化液の分散相は、
約2.5ミクロン又はそれ以下の粒径を有した。
適当な反応器に、完全な乳化液系を撹拌しなが
ら添加した。次いでt−ブチルハイドロパーオキ
サイド70.0ppm(単量体に基づく)を添加した。
得られた媒体を窒素ガスでパージして系から酸素
を除去した。撹拌を継続し、反応容器を約40℃に
維持しながら6時間に亘りメタ亜硫酸ナトリウム
を反応器中へポンプで徐々に送入し、次いで約
100ppm(単量体に基づく)を添加した。得られた
粘稠な乳化液はアクリルアミドが99.49%添加し
たことを示した。
重合体乳化液の安定化は、30%メタ亜硫酸ナト
リウム水溶液78.28部を添加することによつて達
成した。この乳化液を重合条件(40℃で60分間)
下に維持し、残存するアクリルアミドを実質的に
完全に反応させた。この乳化液の0.4%は、重合
体系の安定化を行なう亜硫酸塩を含んでなる。
得られた重合体乳化液に、転化剤混合物とし
て、AMSCO OMS中ビス(2−エチルヘキシ
ル)スルホコハク酸ナトリウムの70%溶液5.5%
及びオクチルフエノール1モル及びエチレンオキ
サイド7.5モルの反応生成物2.0%を30分間に亘つ
て添加した。得られた乳化液を更に1時間40℃に
保つた。この後生成物は均一で粒子を含まなかつ
た。分散重合体相は2.5μ又はそれ以下の粒径を有
した。この標準粘度は表に示す通りであつた。
得られた生成物の標準粘度並びにメトン量及び
熟成度を変えることによる他の生成物の標準粘度
を下表に示す。TABLE Examples 29-38 Emulsion Polymerization of Acrylamide Metone was added to an aqueous acrylamide solution as in Example 1a with stirring for about 5 minutes.
The following steps were then used except that when the PH was 9, sodium hydroxide was added. To a suitable reaction vessel were added 2100.0 parts of acrylamide as a 50.47% aqueous solution and 850.0 parts of deionized water. To this solution are added 2.12 parts of disodium salt of ethylenediaminetetraacetic acid and 72 parts of hydrated ferric sulfate.
% Fe2 ( SO4 ) 3 ) was added at 4.5 parts per 1000 parts H2O . The pH of the resulting solution was adjusted to 5.0. This formed the aqueous monomer phase. The oil phase contains 90.0 parts of sorbitan monooleate,
AMSCO, a bright oily liquid sold by Union Oil Co. of California
Manufactured by dissolving in 1040.0 parts of OMS. The complete oil phase system was added to a suitable high speed homogenizer. The homogenizer was started and the monomer aqueous phase was slowly added to it to form an emulsion with a viscosity of 990 cps. The dispersed phase of the obtained emulsion is
It had a particle size of about 2.5 microns or less. The complete emulsion system was added to a suitable reactor with stirring. Then 70.0 ppm (based on monomer) of t-butyl hydroperoxide was added.
The resulting medium was purged with nitrogen gas to remove oxygen from the system. Sodium metasulfite was gradually pumped into the reactor over a period of 6 hours while stirring was continued and the reaction vessel was maintained at about 40°C, then at about 40°C.
100 ppm (based on monomer) was added. The resulting viscous emulsion showed 99.49% acrylamide loading. Stabilization of the polymer emulsion was achieved by adding 78.28 parts of a 30% aqueous sodium metasulfite solution. Polymerize this emulsion under conditions (40℃ for 60 minutes)
The remaining acrylamide was maintained at a low temperature to allow substantially complete reaction. 0.4% of this emulsion comprises sulfite which stabilizes the polymer system. To the resulting polymer emulsion was added 5.5% of a 70% solution of sodium bis(2-ethylhexyl)sulfosuccinate in AMSCO OMS as a converting agent mixture.
and 2.0% of the reaction product of 1 mole of octylphenol and 7.5 moles of ethylene oxide were added over 30 minutes. The resulting emulsion was kept at 40°C for an additional hour. After this time the product was homogeneous and particle-free. The dispersed polymer phase had a particle size of 2.5 microns or less. This standard viscosity was as shown in the table. The standard viscosity of the product obtained and the standard viscosities of other products by varying the amount of metone and the degree of ripeness are shown in the table below.
【表】【table】
【表】
実施例 39〜42
共重合体の製造
アクリルアミド10重量%を、次の単量体それぞ
れの等重量で代替する以外実施例2の基本的な工
程を繰返した:
(a) アクリル酸
(b) 2−アクリルアミド−2−メチルプロパンア
ンモニウムスルホネート
(c) ジメチルアミノエチルメタクリレートメチル
サルフエート。
(a)及び(b)に対しては、PHを水酸化ナトリウムで
調節した。
メトンを含まない同一の共重合体よりも、対比
しうる改良された結果が観察された。
実施例 43
95/5アクリル酸/アクリルアミド共重合体の
製造
ステンレス鋼ビーカーに、氷アクリル酸(ロー
ム・アンド・ハース社製級)214gを仕込んだ。
磁気撹拌機で撹拌しながら、29%水性アンモニア
(工業用)を添加し、及びPHが7.5になるまで温度
を35℃に保つた(約1.5時間)。蒸留水を添加し
て全量を428gにした。この溶液を1のガラス
製ビーカーに移し、撹拌しながらメトン1.07gを
添加した(アクリル酸に基づいて0.5%)。それは
約10分間で溶解した。次いで50%アクリルアミド
23gを添加し、実施例29〜38の方法に従つて単量
体を乳化重合させた。
標準粘度は5・7センチポイズであつた。
メトンを用いずに上記工程を繰返したとき、標
準粘度は2.9センチポイズ以下であつた。
実施例 44
アクリル酸単独重合体の製造
実施例43の工程を繰返してアクリル酸を単独重
合させた。これは5.2cpsの標準粘度を有した。メ
トンを添加しないとき、標準粘度は2.5cpsであつ
た。
実施例 45〜50
メトンを、下表に示す添加剤の下表に示す量
で代替する以外実施例2の工程を繰返した。ポリ
アクリルアミドを90℃で乾燥した結果も表に示
す。明らかなようにメトンの製造において中間体
でありうるカルボエトキシジメドンナトリウムエ
ノレートは、試験した添加剤のうち最良の結果を
与えた。[Table] Examples 39-42 Preparation of copolymers The basic steps of Example 2 were repeated except that 10% by weight of acrylamide was replaced by equal weights of each of the following monomers: (a) Acrylic acid ( b) 2-Acrylamido-2-methylpropanammonium sulfonate (c) Dimethylaminoethyl methacrylate methyl sulfate. For (a) and (b), the PH was adjusted with sodium hydroxide. Comparable improved results were observed over the same copolymer without metone. Example 43 Preparation of 95/5 Acrylic Acid/Acrylamide Copolymer A stainless steel beaker was charged with 214 g of glacial acrylic acid (Rohm & Haas grade).
While stirring with a magnetic stirrer, 29% aqueous ammonia (technical grade) was added and the temperature was kept at 35° C. until the pH was 7.5 (approximately 1.5 hours). Distilled water was added to bring the total amount to 428 g. This solution was transferred to a glass beaker 1 and 1.07 g of metone (0.5% based on acrylic acid) was added while stirring. It dissolved in about 10 minutes. then 50% acrylamide
23 g was added and the monomers were emulsion polymerized according to the method of Examples 29-38. Standard viscosity was 5.7 centipoise. When the above process was repeated without metone, the standard viscosity was less than 2.9 centipoise. Example 44 Production of acrylic acid homopolymer The process of Example 43 was repeated to homopolymerize acrylic acid. It had a standard viscosity of 5.2 cps. When no metone was added, the standard viscosity was 2.5 cps. Examples 45-50 The process of Example 2 was repeated except that metone was replaced with the additives shown in the table below in the amounts shown below. The results of drying polyacrylamide at 90°C are also shown in the table. Carboethoxydimedone sodium enolate, which can obviously be an intermediate in the production of metone, gave the best results of the additives tested.
【表】
実施例 51
1,3−インダンジオン
メトンを0.05重量%の1,3−インダンジオン
で代替する以外実施例2の方法を繰返した。単量
体は1,3−インタンジオンが禁止剤であつたの
で重合しなかつた。
一方実施例15の方法を繰返して1,3−インダ
ンジオン(0.2%)及び尿素(5.0%)を後段添加
した。即ち添加剤なしに製造した重合体を添加剤
の存在下に乾燥した。90℃での乾燥の結果は次の
通りであつた。
入手状態の粘度 2.9
揮発物 % 7.4
不溶物 % 0.13
即ち不溶物含量は約2%以下であつた。
実施例 52
メルドルムス酸(Meldrums Acid)
PHを変え且つメトンを0.103%のメルドルムス
酸
で代替する以外実施例2の方法を繰返した。
PH4.5及びPH8.0において二つの重合反応を行な
つた。下記のデータから明らかなように、高PH値
の方が改良された生成物が得られた。従つて、
1,3−ジオンは、重合中に存在し及び丁度後段
添加剤として存在しない場合、重合条件下に安定
で効果的であるにちがいないように見えた。
90℃で乾燥した生成物の結果は次の通りであつ
た:
PH4.5 PH8.0
入手状態の粘度 1.4 2.1
揮発物% 9.9 2.1
不溶物% 60.0 38.5
実施例 53〜64
実施例2の基本的な工程に従い、表に示す共
重合体及び単独重合体を製造した。メトンを含ま
ない対照重合体も製造した。
表においてAMDはアクリルアミド;AMPSは
2−アクリルアミド−2−メチルプロパンスルホ
ン酸;ANはアクリロニトリル;及びMAPTAC
は3−(メチルアクリルアミド)プロピルトリメ
チルアンモニウムクロライドである。WNFは生
成物が過せず、従つて不溶物%を決定できなか
つたことを意味する。
実施例57及び58は尿素を5%含有し、10.3%の
固体で行なつた。実施例59〜62は尿素の存在下に
及び13%の固体で行なつた。実施例63及び64は尿
素及びレドツクス系の不存在下に、但しPHを調節
するために水酸化ナトリウムを用いて製造した。
100%のAMPSの実施例63及び64の場合、発熱
℃/分として表示される平均重合速度は次の通り
であることが断熱的に決定された。
実施例 メトン 速度
63 なし 0.07%/分
64 あり 0.14%/分
即ちメトンの使用は重合速度を2倍にした。
実施例53〜62においては、メトンを用いて不溶
物の量を減少させる効果が示される。[Table] Example 51 1,3-Indanedione 0.05% by weight of 1,3-indanedione The method of Example 2 was repeated except that . The monomer did not polymerize because 1,3-intanedione was the inhibitor. On the other hand, the method of Example 15 was repeated, and 1,3-indanedione (0.2%) and urea (5.0%) were added at a later stage. That is, a polymer prepared without additives was dried in the presence of additives. The results of drying at 90°C were as follows. Viscosity as received: 2.9 Volatile % 7.4 Insoluble % 0.13, ie, the insoluble content was about 2% or less. Example 52 Meldrums Acid Meldrums Acid with varying PH and 0.103% of metone The method of Example 2 was repeated except that . Two polymerization reactions were conducted at PH4.5 and PH8.0. As is clear from the data below, higher PH values resulted in improved products. Therefore,
It appeared that the 1,3-dione must be stable and effective under the polymerization conditions if present during the polymerization and not just as a post-additive. The results of the product dried at 90°C were as follows: PH4.5 PH8.0 Viscosity as received 1.4 2.1 % volatile 9.9 2.1 % insoluble 60.0 38.5 Examples 53-64 Basic of Example 2 According to the following steps, the copolymers and homopolymers shown in the table were produced. A control polymer without metone was also prepared. In the table, AMD is acrylamide; AMPS is 2-acrylamido-2-methylpropanesulfonic acid; AN is acrylonitrile; and MAPTAC
is 3-(methylacrylamide)propyltrimethylammonium chloride. WNF means that the product was free and therefore the % insolubles could not be determined. Examples 57 and 58 contained 5% urea and were run at 10.3% solids. Examples 59-62 were conducted in the presence of urea and at 13% solids. Examples 63 and 64 were made in the absence of urea and redox systems, but with sodium hydroxide to adjust the PH. For 100% AMPS Examples 63 and 64, the average polymerization rate expressed as exothermic °C/min was determined adiabatically to be: Example Metone Rate 63 No 0.07%/min 64 Yes 0.14%/min ie the use of metone doubled the polymerization rate. Examples 53-62 demonstrate the effectiveness of using metone in reducing the amount of insoluble matter.
【表】【table】
【表】
実施例 65
メトン0.2%を含有するアクリルアミドの溶液
を製造するために、実施例1(a)の工程を繰返し
た。この溶液を夜通し放置し、次いで活性炭
(Nuchar WV−L 8×30メツシユ)床を通過
させた。
得られた単量体を、メトンを存在させずに上記
実施例2に従つて重合させた。次いで重合体生成
物を90℃で乾燥した。これは入手状態での粘度
2.8を有し、不溶物が2%以下にすぎなかつた。Table: Example 65 The process of Example 1(a) was repeated to prepare a solution of acrylamide containing 0.2% metone. The solution was left overnight and then passed through a bed of activated carbon (Nuchar WV-L 8x30 mesh). The resulting monomer was polymerized according to Example 2 above without the presence of metone. The polymer product was then dried at 90°C. This is the viscosity as received.
2.8, and the insoluble matter was only 2% or less.
Claims (1)
アミド−2−メチルプロパンスルホン酸又はその
塩、或いはそれらの混合物及び式 の1,3−ジオン残基を含有する環式有機化合物
を含んでなる組成物。 2 該1,3−ジオンが単量体の0.001〜2重量
%の量で存在する特許請求の範囲第1項記載の組
成物。 3 共重合されて水溶性の共重合体を生成しうる
更なるエチレン性不飽和の単量体を少くとも1種
含んでなる特許請求の範囲第1項記載の組成物。 4 該1,3−ジオンが重合禁止剤でない特許請
求の範囲第1項記載の重合される組成物。 5 1,3−ジオンが5,5−ジメチル−1,3
−シクロヘキサンジオン又はその互変異性体5,
5−ジメチル−テトラヒドロ−m−レゾルシノー
ルである特許請求の範囲第1〜4項のいずれかに
記載の組成物。 6 1,3−ジオンが1,3−シクロヘキサンジ
オン、フロログリシノール、バルビツル酸、カル
ボメトキシジメドンエノレート及びカルベトキシ
ジメドンエノレートから本質的になる群から選択
される特許請求の範囲第1〜4項のいずれかに記
載の組成物。[Claims] 1. Acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, or a mixture and formula thereof A composition comprising a cyclic organic compound containing a 1,3-dione residue. 2. The composition of claim 1, wherein the 1,3-dione is present in an amount of 0.001 to 2% by weight of the monomers. 3. A composition according to claim 1, comprising at least one further ethylenically unsaturated monomer which can be copolymerized to form a water-soluble copolymer. 4. A polymerizable composition according to claim 1, in which the 1,3-dione is not a polymerization inhibitor. 5 1,3-dione is 5,5-dimethyl-1,3
- cyclohexanedione or its tautomer 5,
The composition according to any one of claims 1 to 4, which is 5-dimethyl-tetrahydro-m-resorcinol. 6. Claim 1, wherein the 1,3-dione is selected from the group consisting essentially of 1,3-cyclohexanedione, phloroglycinol, barbituric acid, carbomethoxydimedone enolate, and carbethoxydimedone enolate. 4. The composition according to any one of items 4 to 4.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8980379A | 1979-10-31 | 1979-10-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5667312A JPS5667312A (en) | 1981-06-06 |
JPH0316363B2 true JPH0316363B2 (en) | 1991-03-05 |
Family
ID=22219654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9579080A Granted JPS5667312A (en) | 1979-10-31 | 1980-07-15 | Composition and manufacture thereof |
Country Status (13)
Country | Link |
---|---|
JP (1) | JPS5667312A (en) |
AU (1) | AU536137B2 (en) |
BR (1) | BR8004823A (en) |
DE (1) | DE3041142A1 (en) |
ES (1) | ES496339A0 (en) |
FI (1) | FI68065C (en) |
FR (1) | FR2468628A1 (en) |
GB (1) | GB2061977B (en) |
IT (1) | IT1149205B (en) |
MX (1) | MX155551A (en) |
NL (1) | NL8003782A (en) |
SE (1) | SE449362B (en) |
ZA (1) | ZA803650B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW318860B (en) * | 1994-03-02 | 1997-11-01 | Mitsui Toatsu Chemicals | |
JP4959683B2 (en) * | 2006-04-06 | 2012-06-27 | 三井化学株式会社 | Method for producing acrylamide |
KR101162810B1 (en) * | 2006-04-06 | 2012-07-05 | 미쓰이 가가쿠 가부시키가이샤 | Method of producing acrylamide |
JP7266055B2 (en) * | 2021-02-19 | 2023-04-27 | Mtアクアポリマー株式会社 | (Meth) acrylamide-based water-soluble polymer powder and method for producing the same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH251651A (en) * | 1945-02-09 | 1947-11-15 | Du Pont | Process for the polymerization of ethylene compounds. |
JPS5265593A (en) * | 1975-11-26 | 1977-05-31 | Mitsubishi Chem Ind Ltd | Preparation of dried water-soluble polymers |
-
1980
- 1980-06-10 SE SE8004327A patent/SE449362B/en not_active IP Right Cessation
- 1980-06-13 GB GB8019483A patent/GB2061977B/en not_active Expired
- 1980-06-17 FI FI801947A patent/FI68065C/en not_active IP Right Cessation
- 1980-06-18 ZA ZA00803650A patent/ZA803650B/en unknown
- 1980-06-18 AU AU59397/80A patent/AU536137B2/en not_active Ceased
- 1980-06-30 NL NL8003782A patent/NL8003782A/en not_active Application Discontinuation
- 1980-07-08 IT IT49194/80A patent/IT1149205B/en active
- 1980-07-15 JP JP9579080A patent/JPS5667312A/en active Granted
- 1980-07-17 MX MX183198A patent/MX155551A/en unknown
- 1980-07-31 BR BR8004823A patent/BR8004823A/en unknown
- 1980-10-22 FR FR8022571A patent/FR2468628A1/en active Granted
- 1980-10-28 ES ES496339A patent/ES496339A0/en active Granted
- 1980-10-31 DE DE19803041142 patent/DE3041142A1/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
FI68065B (en) | 1985-03-29 |
SE8004327L (en) | 1981-05-01 |
ES8202837A1 (en) | 1982-03-01 |
SE449362B (en) | 1987-04-27 |
DE3041142A1 (en) | 1981-08-27 |
IT1149205B (en) | 1986-12-03 |
ES496339A0 (en) | 1982-03-01 |
FI68065C (en) | 1985-07-10 |
NL8003782A (en) | 1981-06-01 |
ZA803650B (en) | 1981-06-24 |
GB2061977A (en) | 1981-05-20 |
BR8004823A (en) | 1981-04-28 |
AU5939780A (en) | 1981-05-07 |
FR2468628B1 (en) | 1983-07-22 |
FR2468628A1 (en) | 1981-05-08 |
FI801947A (en) | 1981-05-01 |
JPS5667312A (en) | 1981-06-06 |
IT8049194A0 (en) | 1980-07-08 |
MX155551A (en) | 1988-03-25 |
AU536137B2 (en) | 1984-04-19 |
GB2061977B (en) | 1983-08-24 |
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