CN100480282C - Acrylic-acid-based homopolymers comprising taurine modified for the treatment of water - Google Patents
Acrylic-acid-based homopolymers comprising taurine modified for the treatment of water Download PDFInfo
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- CN100480282C CN100480282C CNB2004800399618A CN200480039961A CN100480282C CN 100480282 C CN100480282 C CN 100480282C CN B2004800399618 A CNB2004800399618 A CN B2004800399618A CN 200480039961 A CN200480039961 A CN 200480039961A CN 100480282 C CN100480282 C CN 100480282C
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- Prior art keywords
- methyl
- acrylic copolymer
- acid
- polymkeric substance
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 11
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 title description 18
- 229960003080 taurine Drugs 0.000 title description 8
- 229920001519 homopolymer Polymers 0.000 title description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title description 2
- 229940114077 acrylic acid Drugs 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 54
- 229920006243 acrylic copolymer Polymers 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 37
- -1 aminoalkyl sulfonic acid Chemical compound 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 17
- 239000004615 ingredient Substances 0.000 claims description 15
- 230000009435 amidation Effects 0.000 claims description 12
- 238000007112 amidation reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004103 aminoalkyl group Chemical group 0.000 abstract description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 abstract description 3
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 229920000388 Polyphosphate Polymers 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000001506 calcium phosphate Substances 0.000 description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 description 5
- 235000011010 calcium phosphates Nutrition 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- 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 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000003641 microbiacidal effect Effects 0.000 description 4
- 229940124561 microbicide Drugs 0.000 description 4
- 239000002855 microbicide agent Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- SDHMGKANHNMOSS-UHFFFAOYSA-N 1-aminoethanesulfonic acid Chemical compound CC(N)S(O)(=O)=O SDHMGKANHNMOSS-UHFFFAOYSA-N 0.000 description 3
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 239000007983 Tris buffer Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CUWODFFVMXJOKD-UVLQAERKSA-N buserelin Chemical group CCNC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](COC(C)(C)C)NC(=O)[C@@H](NC(=O)[C@H](CO)NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H]1NC(=O)CC1)CC1=CC=C(O)C=C1 CUWODFFVMXJOKD-UVLQAERKSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
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- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 229940050410 gluconate Drugs 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical class OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002719 buserelin Drugs 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- FATUQANACHZLRT-KMRXSBRUSA-L calcium glucoheptonate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O FATUQANACHZLRT-KMRXSBRUSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002300 glucoheptoses Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- HPEUEJRPDGMIMY-IFQPEPLCSA-N molybdopterin Chemical compound O([C@H]1N2)[C@H](COP(O)(O)=O)C(S)=C(S)[C@@H]1NC1=C2N=C(N)NC1=O HPEUEJRPDGMIMY-IFQPEPLCSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to (meth)acrylic acid copolymers comprising methacrylic acid units. The polymer is functionalised with aminoalkyl sulphonic acids. The invention also relates to a method for the production thereof and to the use thereof for treating water, preventing scale during the extraction of oil, and for preventing corrosion in aqueous systems.
Description
(methyl) acrylic copolymer that the present invention relates to the method for a kind of preparation (methyl) acrylic copolymer, obtains by this method and be used for water treatment, the preferred purposes in cooling and heat-processed and in oil production, suppress the purposes of fouling.
In oil production, because the precipitation of alkaline earth metal carbonate and sulfonate appears in mixing of temperature variation and oil-field water and injection water in the production process.They have stopped up the rock stratum hole and have accumulated in pipe surface, cause producing being difficult to carry out, even can not carry out sometimes.
In water treatment, in cooling or heat-processed (comprising sea water desalinization), or in heat transfer process, generally in cooling or heating medium, add respectively and can prevent or corrosion and sedimentary ingredients occur in the delay loop at least greatly.The ingredients of Shi Yonging comprises zinc salt, polyphosphate, phosphonate, polymkeric substance, microbicide and/or tensio-active agent as required for this reason.
In order to control protection against corrosion and the resistive connection dirt in the open cooling loop, there is difference in principle in two kinds of methods:
At first, phosphorous ingredients can be used for cooling and heating medium.Representative instance wherein is polyphosphate and phosphonate, 1-hydroxyl ethane-1 for example, and 1-di 2 ethylhexyl phosphonic acid (HEDP), 2-phosphoryl butane-1,2,4-tricarboxylic acid (GBTC) and Amino Trimethylene Phosphonic Acid (ATMP) are used with the form of its sodium salt separately.These phosphorous ingredients generally influence hardness stability.In addition, polyphosphate has improved corrosion-resisting function.
Perhaps as selection, zinc salt also can be used for cooling and heating medium, and in the case, wherein the zine ion of Cun Zaiing is mainly used in the protection iron and steel.
In some cases, also a spot of zinc salt is added in the phosphonate, so that protect employed iron and steel simultaneously outside hardness stability.The effect of these additives strengthens by suitable polymers:
Suitable polymers at first can strengthen the effect of phosphonate to hardness stability, and secondly, they can also stablize polyphosphate, especially when they add with high density.Prevented calcium phosphate precipitation like this.In addition, suitable polymers can also be stablized zn cpds, thereby can not occur deposition on the metallic surface, and the destruction to protective membrane therefore do not occur.Anticorrosive work is that example is passed through in the metallic surface the film forming fact and explained in order to phosphonate.This film is isolated iron and steel and cooling or heating medium.Formed film is made up of the phosphonate of most iron (II) and calcium ion and introducing.This film is extremely thin, makes stabilization must guarantee to prevent to break and the corrosive possibility occurs at each point.
Be applicable to and stablize phosphonate and phosphatic polymkeric substance can be known by prior art in principle.
Thereby for example, EP-A 0 244 584 has described the N-substituted acrylamide that for example carries sulfo group buserelin group and has been used to suppress industrial cooling loop and corrosion occurred.The acrylamide that these N-replace is by the transamidation preparation of polypropylene acid amides.N-substituted acrylamide according to EP-A 0 244 584 produces inhibition to phosphate anion, but phosphonium acid ion is not had restraining effect.
EP-B 0 330 876 has described on the structure and EP-A 0 244 584 similar N-substituted acrylamides.But desired as EP-B 0 330 876, the purposes of these N-substituted acrylamides relates to stablizes iron in water-based system, wherein do not disclose the definite degree of amidation of used N-substituted acrylamide.
US 4,801, and 388 polymkeric substance of having described by adding based on (methyl) vinylformic acid and sulfo group alkyl (methyl) acrylamide or methyl (acrylamide) suppress sedimentary method in water-based system.
US 4,604,431 described a kind of by comprising the acrylic or methacrylic acid groups polymkeric substance and the method for alkylsulphonic acid prepared in reaction acrylamide alkyl sulfonic acids under pressure and elevated temperature.
US 4,756, and 881 disclose and comprise the combination of acrylamido alkansulfonic acid and organophosphate and be used for suppressing the corrosive purposes at industrial colling.
The shortcoming of above-mentioned prior art polymers is that they precipitate under higher calcium concn.In addition, particularly unite under the situation of using phosphonium acid ion and zine ion in cooling or heating systems, such polymkeric substance is favourable: it plays a role simultaneously to stablize both modes of phosphate anion and zine ion.In addition, when using phosphate additive, and particularly when calcium ion exists with higher concentration, the polymkeric substance that can suppress calcium phosphate precipitation is favourable.At last, such polymkeric substance conforms with expectation, and it generally disperses with solid particulate, thereby has avoided them to deposit on the metallic surface of cooling or heating systems.The prior art polymkeric substance does not satisfy or has only satisfied deficiently these requirements.
Therefore, the purpose of this invention is to provide a kind of method for preparing polymkeric substance, this polymkeric substance is in cooling or heating circuit, in corresponding medium, strengthen the hardness stabilization of phosphonate and stablized polyphosphate simultaneously, thereby, for example, precipitation does not appear in the presence of calcium ion.And the polymkeric substance that obtains by the inventive method is used for stablizing zn cpds, so that they can not form deposition on the metallic surface of cooling or heating circuit.
According to the present invention, the method for preparation (methyl) acrylic copolymer of described purpose by comprising following processing step realizes:
(1) (methyl) vinylformic acid carries out radical polymerization, forms polymkeric substance I, and
(2) by making the polymkeric substance I amidation that forms by processing step (1) with at least a amidoalkanesulfonic acid reaction.
In the processing step (2) of the inventive method, the carboxylate radical of the polymkeric substance I that is formed by processing step (1) and the ratio of aminoalkyl group sulfonic acid are preferably 2:1-15:1, preferred especially 3:1-11:1, especially 4:1-8:1.
Processing step (1) preferably 100-200 ℃, preferred especially 105-135 ℃, especially carry out under 120-125 ℃.
Processing step (1) preferably carries out in closed reaction container such as autoclave.Therefore, the pressure of processing step (1) is generally determined by the vapour pressure (autogenous pressure) of used component under said temperature.Irrelevant with it, if suitable, can use the pressure of additional pressure or reduction.
Described monomeric radical polymerization is preferably using hydrogen peroxide as carrying out under the initiator.But,, can select to use all compounds that can under reaction conditions, form free radical, for example superoxide, hydroperoxide, sulfuric peroxide hydrochlorate, peroxidation dicarboxylic acid, peroxycarboxylic acid esters and/or azo-compound about initiators for polymerization.
If suitable, in the processing step (1) of the inventive method, can use other other monomer, for example can with the ethylene linkage unsaturated monomer of (methyl) acrylic acid copolymer.Suitable copolymers is a monoene key unsaturated carboxylic acid for example, as toxilic acid, fumaric acid, methylene-succinic acid, methylfumaric acid, methylene radical propanedioic acid and citraconic acid.But the monomer of other copolymerization is the C of monoene key unsaturated carboxylic acid
1-C
4Alkyl ester, for example methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 and vinylformic acid hydroxy butyl ester.In addition, suitable comonomer is by polyoxyethylene glycol deutero-(methyl) the polyalkylene glycol acrylate alkyl ester with 2-50 ethylene glycol unit, has the polyoxyethylene glycol of 2-50 ethylene glycol unit and an alkyl oxide of vinyl carbinol.Other suitable monomer is an acrylamide, Methacrylamide, the N-vinyl formamide, vinylbenzene, vinyl cyanide, methacrylonitrile and/or carry sulfonic monomer and vinyl-acetic ester, propionate, the phosphonic acids allyl ester, the N-vinyl pyrrolidone, the N-caprolactam, the N-vinyl imidazole, N-vinyl-glyoxal ethyline quinoline, the chlorination diallyl dimethyl ammonium, dimethylaminoethyl acrylate, the vinylformic acid lignocaine ethyl ester, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.Alkalescence monomer such as dimethylaminoethyl methacrylate can be used as comonomer, for example with the form of alkali, and as the salt that forms with strong acid, as the salt that forms with hydrochloric acid, sulfuric acid or phosphoric acid, or with the form of quaternary ammonium compound.Equally, the form that the above-mentioned monomer that contains acidic group can free acid or as salt for example sodium, potassium or ammonium salt is used for described polyreaction.
The inventive method is preferably carried out in the following manner: (methyl) acrylic copolymer has the sulfonate groups that comprises counterion, and counterion wherein is selected from proton, alkalimetal ion or ammonium ion.But the electric charge of the sulphonate-base of described (methyl) acrylic copolymer generally can be saturated with any desired counterion.
Can preferably obtain as polymers soln by the polymkeric substance I that the inventive method processing step (1) obtains, its solid content that has is preferably 10-70%, preferred especially 30-60%, especially 45-55%.
In the particular embodiment of the inventive method, polymkeric substance I carried out amidation in processing step (2) before, the pH regulator that will comprise the polymers soln of polymkeric substance I was preferred 2.0-9.0, preferred especially 4.0-7.5, especially 4.5-6.5.The alkali that is applicable to this is all alkali in principle, but the aqueous solution of preferred alkali metal hydroxide, for example aqueous sodium hydroxide solution.
Amidation (processing step (2)) is preferably carried out under protective atmosphere, for example uses argon gas or nitrogen.
The processing step of the inventive method (2) preferably 140-250 ℃, preferred especially 165-200 ℃, especially carry out under 175-185 ℃.The monomeric unit among the polymkeric substance I and the mol ratio of amidoalkanesulfonic acid are preferably 15:1-2:1, preferred especially 11:1-3:1, especially 8:1-4:1.The pressure of processing step (2) is preferably the 1-25 crust, preferred especially 5-17 crust, especially 7-13 crust.
In the particular embodiment of the inventive method, as aminoalkyl sulfonic acid, use aminoethane sulfonic acid, therefore the polymkeric substance that is obtained by processing step (2) has the unit based on aminoethane sulfonic acid.But other any aminoalkyl sulfonic acid also can use.In this with reference to above-mentioned reason.
The preferred random distribution of sulfo group alkylamide structural unit of being produced by the processing step (2) of the inventive method is in (methyl) acrylic copolymer.
Influence to the type decided of the Raolical polymerizable in the processing step (1) sulfo group alkylamide unit between single polymer molecule and along the distribution of polymer chain.Thereby with monomeric free-radical polymerized the comparing by corresponding construction, general acquisition has the mixture of the polymer chain of different structure.Therefore, the polymkeric substance by similar polymkeric substance mode (polymer-analogous means) preparation can with undertaken by basic copolymerization by monomer acrylamide and vinylformic acid, to make amide units change the polymkeric substance of amidated acquisition with aminoalkyl sulfonic acid then significantly different.And, vinylformic acid, the commentaries on classics amidate action free-radical polymerized and subsequently of lactonic acid (terelactone acid) and acrylamide is generally caused other structure.In the end under the polyreaction situation of Miao Shuing, the unitary distribution of sulfo group alkylamide is pre-determined by the monomeric copolymerization parameter that uses in the free radicals copolymerization reaction.The result be polymkeric substance by similar polymkeric substance mode synthetic situation under different functional groups general different at the distribution statistics on the main polymer chain with the distribution statistics when corresponding group passes through free-radical polymerized introducing.
The invention further relates to (methyl) acrylic copolymer that obtains by aforesaid method.
These (methyl) acrylic copolymer preferably comprise
(a) poly-(methyl) vinylformic acid basis structure of 30-95 weight %, preferred 40-90 weight %, preferred especially 60-80 weight %,
(b) the amide units of 5-70 weight %, preferred 10-60 weight %, preferred especially 20-40 weight % based on aminoalkyl sulfonic acid,
Wherein the unit gross weight in (methyl) acrylic copolymer is 100 weight %, and all wt per-cent is based on (methyl) acrylic copolymer.
(methyl) of the present invention acrylic copolymer, even in substoichiometric scope prevents that too much calcium ion from penetrating into the film on the metallic surface in for example cooling or the heating circuit.
The weight-average molecular weight of (methyl) of the present invention acrylic copolymer is preferably 1000-20 000g/mol, preferred especially 1500-10 000g/mol, especially 2000-6000g/mol.Here, weight-average molecular weight utilize gel permeation chromatography (=GPC) at room temperature use moisture eluant to measure.
The present invention's (methyl) acrylic copolymer has preferred 5-50, preferred especially 8-35, the K value of 11-16 especially.Described K value is utilized the Fikentscher method, and (ISO174 DIN53726) measures.
If suitable, the present invention's (methyl) acrylic copolymer can comprise in addition other can with the ethylene linkage unsaturated monomer unit of (methyl) acrylic acid copolymer.To this suitable monomers is for example ethylene linkage unsaturated carboxylic acid, for example toxilic acid, fumaric acid, methylene-succinic acid, methylfumaric acid, methylene radical propanedioic acid and citraconic acid.But the monomer of other copolymerization is the C of monoene key unsaturated carboxylic acid
1-C
4Alkyl ester, for example methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 and vinylformic acid hydroxy butyl ester.In addition, suitable comonomer is by polyoxyethylene glycol deutero-(methyl) the polyalkylene glycol acrylate alkyl ester with 2-50 ethylene glycol unit, has the polyoxyethylene glycol of 2-50 ethylene glycol unit and an alkyl oxide of vinyl carbinol.Other suitable monomers is an acrylamide, Methacrylamide, the N-vinyl formamide, vinylbenzene, vinyl cyanide, methacrylonitrile and/or carry sulfonic monomer and vinyl-acetic ester, propionate, the phosphonic acids allyl ester, the N-vinyl pyrrolidone, the N-caprolactam, the N-vinyl imidazole, N-vinyl-glyoxal ethyline quinoline, the chlorination diallyl dimethyl ammonium, dimethylaminoethyl acrylate, the vinylformic acid lignocaine ethyl ester, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.Alkalescence monomer such as dimethylaminoethyl methacrylate can be used as comonomer, for example with the form of alkali, and as the salt that forms with strong acid example hydrochloric acid, sulfuric acid or phosphoric acid, or with the form of quaternary ammonium compound.Equally, the form that the above-mentioned monomer that contains acidic group can free acid or as salt for example sodium, potassium or ammonium salt is used for described polyreaction.
Amide units based on aminoalkyl sulfonic acid can be derived by any desired aminoalkyl sulfonic acid.Specially suitable aminoalkyl sulfonic acid is to have those of 2-12, preferred 4-10 carbon atom.Described amino can be primary, the second month in a season or uncle's amino.About other substituting group, described aminoalkyl sulfonic acid can have for example hydroxyl or alkoxy or halogen atom.Alkyl can be saturated, or preferably undersaturated, and is nonbranched or branching, or is connected to form ring.Described amino can be arranged in the aminoalkyl chain or as branch substituting group or end substituting group.They can also be the integral parts of preferred saturated heterocyclic.
In preferred implementation of the present invention, the present invention's (methyl) acrylic copolymer comprises the structural unit (II) based on aminoethane sulphonic acid (taurine):
Usually, the electric charge of the sulphonate-base of (methyl) acrylic copolymer can be saturated with any desired counterion.Preferably, counterion is selected from proton, alkalimetal ion or ammonium ion.
The preferred random distribution of sulfo group alkylamide structural unit is in (methyl) acrylic copolymer.
The present invention's (methyl) acrylic copolymer is obviously different with prior art (methyl) acrylic copolymer that can pass through with aminoalkyl sulfonic acid (methyl) acrylamide polymer commentaries on classics accordingly amidation acquisition on the binding mode of water treatment, resistive connection dirt and corrosion prevention.
The characteristic of this binding mode is the preferred random distribution owing to sulfo group alkylamide structural unit.Polycarboxylic direct amidation influences sulfo group buserelin unit fatefully between single polymer molecule and along the distribution of polymer chain.Thereby, uniquely, obtain to have and pass through the polymer chain mixture of the monomeric free-radical polymerized different structure of corresponding construction.Therefore, by similar polymkeric substance mode synthetic polymkeric substance for example with undertaken by monomer acrylamide and vinylformic acid free-radical polymerized, with aminoalkyl group sulfonic acid amide units to be changeed the polymkeric substance that amidation obtains then significantly different.In the end under the polyreaction situation of Miao Shuing, the unitary distribution of sulfo group buserelin is pre-determined by the monomeric copolymerization parameter that uses in the free radicals copolymerization reaction.The result be by free-radical polymerized acquisition polymkeric substance with compare by the similar polymkeric substance mode of corresponding group being introduced in the synthetic polymkeric substance in advance, the distribution of different functional groups on main polymer chain is obviously different.
In addition, the present invention relates to a kind of method of in water-based system, stablizing phosphoric acid salt, phosphonate and/or zine ion (for example zinc chloride or zinc phosphate), wherein with at least a the present invention (methyl) acrylic copolymer and/or at least aly can add described system by (methyl) acrylic copolymer that the inventive method obtains.The amount of described polymkeric substance in water-based system is preferably 5-200ppm, preferred especially 5-50ppm, and 10-40ppm especially, described amount is in all cases all based on water-based system.
Polymkeric substance of the present invention can directly be metered in the water-based system or as introducing with the mixture of another kind of component via one or more stoichiometric points.
The present invention described above (methyl) acrylic copolymer and/or can be used for water treatment by (methyl) acrylic copolymer that the inventive method obtains, resistive connection dirt and/or in water-based system, suppress corrosion in oil production.
If suitable, it is favourable using the present invention's (methyl) acrylic copolymer with the ingredients form.Therefore, the invention further relates to be used for water treatment, at oil production resistive connection dirt and/or be used to suppress the corrosive ingredients, it comprises at least a (methyl) acrylic copolymer of the present invention and/or at least a (methyl) acrylic copolymer that can obtain by the inventive method.If suitable, ingredients of the present invention comprises other composition.Except that other ingredients composition such as tensio-active agent, dispersion agent, defoamer, corrosion inhibitor, oxygen scavenqer and microbicide, such ingredients composition for example is:
A) linearity of condensation and ring-type polyphosphate, for example Tri sodium Phosphate, Sodium hexametaphosphate 99;
B) phosphonate, 2-phosphinylidyne butane-1,2 for example, the 4-tricarboxylic acid, amino three-(methylene phosphonic acid), 1-hydroxy ethylene (1, the 1-di 2 ethylhexyl phosphonic acid), ethylenediamine tetramethylene phosphonic acid, hexamethylene-diamine tetramethylene phosphonic acid or diethylenetriamine pentamethylenophosphonic acid(DTPP);
C) aminocarboxylic acid ester, nitrilotriacetic acid(NTA) for example, ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA), hydroxyethyl ethylene amine triacetic acid, methylglycine oxalic acid, gluconate (gluconate), glucoheptose salt (glucoheptonate), quadrol disuccinate and imido grpup disuccinate;
D) water-soluble polymers, for example homopolymer of sulfonated monomers and multipolymer, 2-acrylamido-2-methyl propane sulfonic acid for example, weight-average molecular weight is styrene sulfonic acid or the vinyl sulfonic acid of 500-15 000, or naphthene sulfonic acid-formaldehyde condensation products.
The ingredients that comprises inhibition or polymer dispersion can directly add water-based system by one or more stoichiometric points.
The present invention will be that the basis is set forth with following embodiment.
Embodiment:
1) prepares polymkeric substance of the present invention
Prepare polymkeric substance (processing step (1)) by vinylformic acid.
A) in the reactor with nitrogen inlet, reflux exchanger and measuring instrument, the mixture heating up with 394g distilled water and 5.6g phosphoric acid (concentration 50%) under supplying with nitrogen and stirring is 95 ℃ to internal temperature.Then, add (1) 936g vinylformic acid continuously in 5 hours time, (2) 280g Sodium Persulfate solution (concentration 10%) and (3) 210g concentration are the SODIUM HYDROSULPHITE sodium water solution of 40 weight %.Be that 95 ℃ were further stirred down after one hour, also passed through the reaction mixture cool to room temperature to add the aqueous sodium hydroxide solution of 169g concentration 50% with pH regulator to 4.0.
Obtain a kind of transparent polymers soln, its solid content is 54 weight %, and the K value is 25 (aqueous solution of concentration 1 weight %, 25 ℃).
B) 1000g is packed in the reaction vessel of pressure-stabilisation from the polymers soln (solid content=50%) of step a) and the mixture of 130.47g taurine (aminoethane sulphonic acid), this reaction vessel is equipped with agitator, nitrogen inlet, temperature sensor, pressure display unit and ventilation installation.The aqueous sodium hydroxide solution that in this mixture, adds 110g concentration 50%.This equipment also seals for three times with nitrogen wash.Then, under agitation with the internal temperature of this mixture heating up to 180 ℃.In this process, set up the pressure of about 10 crust.Mixture kept 5 hours under this temperature.There is not cooling mixture under the expansion then.Open this equipment and with pH regulator to 7.2.Produced a kind of yellow transparent solution like this, its solid content is 49.6%, and the K value is 14.6 (in 3% NaCl solution, concentration 1%).
2) prepare comparative polymer by changeing amidation
A) in reactor with nitrogen inlet, reflux exchanger and measuring instrument, pack into earlier 180g distilled water and supply with nitrogen and stir under be heated to reflux temperature.Close nitrogen gas stream, in 5 hours time, add (1) 180.15g vinylformic acid, (2) 35.55g acrylamide, the aqueous hydrogen peroxide solution of (3) 143.8g concentration 30% and (4) 21.6g mercaptoethanol (the concentration 10 weight % aqueous solution) then abreast continuously.Be further to stir under the reflux temperature after 2 hours, the reaction mixture cool to room temperature is also passed through to add the aqueous sodium hydroxide solution of 169g concentration 50% with pH regulator to 4.0.
Having obtained a kind of solid content is that 18.2 weight % and K value are polyacrylamide [16.6 moles of %]-vinylformic acid clear solution of 11.5 (the concentration 1 quality % aqueous solution, 25 ℃).
B) preparation procedure with patent EP0 330 876 B1 embodiment 1 is that amidation is changeed on the basis, regulates COOH and SO in the product
3The ratio of H so that polymkeric substance and embodiment 1 quite (content of taurine in two kinds of polymkeric substance is identical; pH is brought up to 6 for improving conversion rate): 500g is packed in the reaction vessel of pressure-stabilisation from the polymers soln (solid content=18.2%) of step a) and the mixture of 27.7g taurine (aminoethane sulphonic acid), and this reaction vessel is equipped with agitator, nitrogen inlet, temperature sensor, pressure display unit and ventilation installation.The aqueous sodium hydroxide solution that in this mixture, adds 76.7g concentration 50%.This equipment also seals for three times with nitrogen wash.Then, under agitation with the internal temperature of this mixture heating up to 150 ℃.In this process, set up the pressure of about 10 crust.Mixture kept 4 hours under this temperature.There is not cooling mixture under the expansion then.Open this equipment and with pH regulator to 7.2.Obtain a kind of yellow transparent solution, its solid content is 25.4%, and the K value is 13.9 (in 3% NaCl solution, concentration 1%).
3) polymkeric substance is used to suppress the purposes of calcium phosphate and phosphonic acids calcium
A) suppress calcium phosphate
Principle be test be used for cooling loop the active equipment of inhibition of polymkeric substance: Dr.Lange photometer, model LP2W
435nm filter paper
Be equipped with the suction strainer instrument of 0.45 μ m membrane filter paper
Shake water-bath (GFL model 1083)
300ml Lupolen beaker (salable)
Disposable Glass tubing (4ml, Ratiolab)
The Sartorius balance, model LC4800-P
Reagent: vanadate/molybdate-be used to measure phosphatic reagent (Merck)
Testing liquid A: be formulated into 1 liter 0.42gH with distilled water
3PO
4Solution (5%)
The CaCl of testing liquid B:1.64g/l
2.6H
2O
0.79g/l MgSO
4.7H
2O
1.08g/l NaHCO
3
Polymers soln: concentration 1%, based on active substance
Program: A puts into the Lupolen beaker with the 100ml testing liquid, is metered into the polymers soln (10-20ppm) of 2-4ml concentration 0.1%, adds 100ml testing liquid B then.Behind sealed beaker, be placed on 70 ℃ shake in the water-bath 24 hours.After cooling (about 1 hour), by passing membrane filter paper (0.45 μ m) suction strainer filtering testing liquid.Get the solution after 50ml filters then, measure phosphatic residual volume by adding 10ml vanadate/molybdate reagent.After 10 minutes reaction times, can utilize photometer is the phosphatic content of fundamental measurement with the working curve.
The concentration of testing liquid: GH=5.4mmol/l
KH＝6.42mmol/l
PO
4＝10ppm
Polymkeric substance=10-20ppm active substance
Table: suppress [%]
| Dosage (ppm) | 15 | 20 | 25 |
| Taurine modified polymkeric substance (according to the present invention) | 90 | 96 | 100 |
| Change amidated polymkeric substance (not according to the present invention) | 38 | 96 | 100 |
B) suppress phosphonic acids calcium
Principle be test be used for cooling loop the inhibition activity of polymkeric substance
Equipment: Dr.Lange photometer, model LP2W 800nm filter paper
Be equipped with the suction strainer instrument of 0.45 μ m membrane filter paper
Shake water-bath (GFL model 1083)
300ml Lupolen beaker (salable)
Dr.Lange sample case LCK350
The Sartorius balance, model LC 4800-P
Reagent: testing liquid A:
2.2g/l HEDP concentration 1% WS (Dequest 2010) or 5.7g/l PBTC concentration 1%WS (Bayhibit AM) or 2.1g/l ATMP concentration 1% WS (Dequest 2000) are formulated into 1 liter with distilled water
The CaCl of testing liquid B:1.64g/l
2.6H
2O
0.79g/l MgSO
4.7H
2O
1.08g/l NaHCO
3
0.1% polymers soln is based on active substance
Program: A puts into the Lupolen beaker with the 100ml testing liquid, adds the polymers soln (10-20ppm) of 2-4ml concentration 0.1%, adds 100ml testing liquid B then.Behind sealed beaker, be placed on 70 ℃ shake in the water-bath 24 hours.After cooling (about 1 hour), by passing membrane filter paper (0.45 μ m) suction strainer filtering testing liquid.Utilize Dr.Lange sample case LCK350 to measure repressed phosphonate amount then.
The concentration of testing liquid: GH=5.4mmol/l
KH＝6.42mmol/l
PO
4＝10ppm
Polymkeric substance=10-20ppm active substance
Table: suppress [%]
| Dosage (ppm) | 10 | 20 | 30 |
| Taurine modified polymkeric substance (according to the present invention) | 68 | 94 | 100 |
| Change amidated polymkeric substance (not according to the present invention) | 52 | 84 | 89 |
Changeing the amidation polymkeric substance is the terpolymer of AA, acrylamide and acrylamido ethane sulfonic acid.With commentaries on classics amidation polymer phase ratio, polymkeric substance of the present invention inhibition to calcium phosphate in than the low dosage scope strengthens.Should activity when using especially remarkable with not enough stoichiometry.
4) be used for the ingredients example of water treatment, particularly water coolant
A) polymkeric substance/zinc ingredients (not phosphorous hydrochlorate)
| i) | Polymkeric substance of the present invention | 40％ | (resistive connection dirt, zinc is stable) |
| ii) | Zinc chloride | 25％ | (anticorrosive) |
| iii) | Tolytriazole | 0.5％ | (anticorrosive) |
| iv) | Defoamer | 2％ | (moistening) |
| v) | Microbicide | (controlling microbial) |
B) organic ingredients (not phosphorous hydrochlorate and heavy metal)
| i) | Polymkeric substance of the present invention | 20-25％ | (phosphonate is stable, and mud disperses) |
| ii) | Phosphonate (HEDP+PBTC) | 10-20％ | (the resistive connection dirt suppresses corrosion) |
| iii) | Tolytriazole | 2-5％ | (anticorrosive) |
| iv) | Defoamer | 1-3％ | (moistening) |
| v) | Microbicide | (controlling microbial) |
HEDP=1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, sodium salt
PBTC=2-phosphinylidyne butane-1,2,4-tricarboxylic acid, sodium salt
C) phosphoric acid salt/phosphonate ingredients
| i) | Polymkeric substance of the present invention | 20％ | (suppress phosphoric acid salt, suppress phosphonate) |
| ii) | Phosphoric acid salt/phosphonate | 5-15％ | (anticorrosive, resistive connection dirt) |
| iii) | Tolytriazole | 2-5％ | (anticorrosive) |
| iv) | Defoamer | 1-3％ | (moistening) |
3) measure molecular-weight average
Weight-average molecular weight utilize gel permeation chromatography (=(the 0.08m TRIS buffer reagent (TRIS=three (methylol) aminomethane) with pH=7 is at distilled water+0.15m NaCl+0.01mNaN GPC) at room temperature to make the use eluant
3In) measure.The concentration c that sample has=0.1 quality %.And the injection volume is V
Inject=200 μ L.Use the sodium polyacrylate calibration mixture of wide distribution to calibrate.The chromatographic column combination is made up of Waters Ultrahydrogel 1000,500,500 and TSK PW-XL5000 (from Tosohaas).Use difference formula refractometer to survey.
Claims (8)
1. method for preparing (methyl) acrylic copolymer, this method comprises following processing step:
(1) (methyl) vinylformic acid carries out radical polymerization, forms polymkeric substance I, and
(2) by making the polymkeric substance I amidation that is formed by processing step (1) with at least a amidoalkanesulfonic acid reaction, wherein the mol ratio of monomer among the polymkeric substance I and amidoalkanesulfonic acid is that 8:1-4:1 and described (methyl) acrylic copolymer comprise
(a) poly-(methyl) vinylformic acid basis structure of 30-95 weight %,
(b) the amide units of 5-70 weight % based on aminoalkyl sulfonic acid,
Wherein the unit gross weight in (methyl) acrylic copolymer is 100 weight %, and all wt per-cent is based on (methyl) acrylic copolymer, and wherein sulfo group alkylamide structural unit randomly is distributed in (methyl) acrylic copolymer.
2. the method for claim 1, wherein processing step (1) carries out under 100-200 ℃.
3. method as claimed in claim 1 or 2, wherein processing step (2) carries out under 140-250 ℃.
4. pass through (methyl) acrylic copolymer of method acquisition as claimed in claim 1 or 2.
5. (methyl) as claimed in claim 4 acrylic copolymer, wherein the weight-average molecular weight of (methyl) acrylic copolymer is 1000-20000g/mol.
6. a method of stablizing phosphoric acid salt and/or phosphonate and/or zine ion in water-based system is wanted 4 described (methyl) acrylic copolymer comprising adding as right in described system.
7. (methyl) as claimed in claim 4 acrylic copolymer is used for water treatment, suppresses fouling and/or suppress the corrosive purposes in water-based system in oil production.
8. one kind is used for water treatment, suppresses fouling and/or suppress the corrosive ingredients in oil production, and it comprises (methyl) as claimed in claim 4 acrylic copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10352457.6 | 2003-11-07 | ||
| DE10352457A DE10352457A1 (en) | 2003-11-07 | 2003-11-07 | Acrylic acid-based homopolymers with taurine modified for water treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1902239A CN1902239A (en) | 2007-01-24 |
| CN100480282C true CN100480282C (en) | 2009-04-22 |
Family
ID=34559549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800399618A Expired - Fee Related CN100480282C (en) | 2003-11-07 | 2004-11-05 | Acrylic-acid-based homopolymers comprising taurine modified for the treatment of water |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1682590A1 (en) |
| CN (1) | CN100480282C (en) |
| CA (1) | CA2544771A1 (en) |
| DE (1) | DE10352457A1 (en) |
| WO (1) | WO2005044868A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10689280B2 (en) * | 2009-12-31 | 2020-06-23 | Ecolab Usa Inc. | Method for the removing and reducing scaling |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640793A (en) * | 1984-02-14 | 1987-02-03 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604431A (en) * | 1985-11-22 | 1986-08-05 | Nalco Chemical Company | Chemical modification of (meth)acrylic acid homopolymers and alkyl (meth)acrylate polymers in aqueous systems with amino sulfonic acids |
| DE10015135A1 (en) * | 2000-03-29 | 2001-10-04 | Basf Ag | Process for modifying polymers containing acid groups |
| DE10320388A1 (en) * | 2003-05-06 | 2004-11-25 | Basf Ag | Polymers for water treatment |
-
2003
- 2003-11-07 DE DE10352457A patent/DE10352457A1/en not_active Withdrawn
-
2004
- 2004-11-05 WO PCT/EP2004/012542 patent/WO2005044868A1/en active Application Filing
- 2004-11-05 EP EP04797652A patent/EP1682590A1/en not_active Withdrawn
- 2004-11-05 CA CA002544771A patent/CA2544771A1/en not_active Abandoned
- 2004-11-05 CN CNB2004800399618A patent/CN100480282C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640793A (en) * | 1984-02-14 | 1987-02-03 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005044868A1 (en) | 2005-05-19 |
| DE10352457A1 (en) | 2005-06-09 |
| EP1682590A1 (en) | 2006-07-26 |
| CA2544771A1 (en) | 2005-05-19 |
| CN1902239A (en) | 2007-01-24 |
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