CN101155882A - Copolymer comprising monoethylenically unsaturated dicarboxylic acid derivatives - Google Patents
Copolymer comprising monoethylenically unsaturated dicarboxylic acid derivatives Download PDFInfo
- Publication number
- CN101155882A CN101155882A CNA2006800034444A CN200680003444A CN101155882A CN 101155882 A CN101155882 A CN 101155882A CN A2006800034444 A CNA2006800034444 A CN A2006800034444A CN 200680003444 A CN200680003444 A CN 200680003444A CN 101155882 A CN101155882 A CN 101155882A
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- structural unit
- alkyl
- carbon atom
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims description 12
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 51
- 150000001412 amines Chemical class 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 23
- 230000007797 corrosion Effects 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 22
- 229920002367 Polyisobutene Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000004922 lacquer Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 7
- 230000000996 additive effect Effects 0.000 claims 3
- 229920000642 polymer Polymers 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 42
- 150000001721 carbon Chemical group 0.000 description 21
- -1 alkyl vinyl ether Chemical compound 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012972 dimethylethanolamine Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NEDKAGCGCJOBNQ-UHFFFAOYSA-N n-hydroxypropanethioamide Chemical compound CCC(=S)NO NEDKAGCGCJOBNQ-UHFFFAOYSA-N 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000012812 general test Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CFEYBLWMNFZOPB-UHFFFAOYSA-N pent-4-enenitrile Chemical compound C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003556 thioamides Chemical group 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- UBYWYEGPDNYPHZ-UHFFFAOYSA-N 2-hydroxyethyl but-2-enoate Chemical compound CC=CC(=O)OCCO UBYWYEGPDNYPHZ-UHFFFAOYSA-N 0.000 description 1
- GWSQQDUFKKYTCA-UHFFFAOYSA-N 2-hydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCC(C)O GWSQQDUFKKYTCA-UHFFFAOYSA-N 0.000 description 1
- IHXNSHZBFXGOJM-UHFFFAOYSA-N 2-methylbut-2-enenitrile Chemical compound CC=C(C)C#N IHXNSHZBFXGOJM-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- BVVBDOGXOITVSY-UHFFFAOYSA-N 4-hydroxybutyl but-2-enoate Chemical compound CC=CC(=O)OCCCCO BVVBDOGXOITVSY-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical class OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229920002368 Glissopal ® Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a polymer comprising dicarboxylic acid unit changed by SR, -CSNR2 and/or -CN and at least one other polymer. The invention also discloses a method for producing the polymer by using the reaction of similar polymers, and the use of the polymer as inhibitor.
Description
The present invention relates to comprise the dicarboxylic acid units of modification and the multipolymer of at least a other comonomers.The present invention additionally relate to a kind of by being similar to polymkeric substance their method of prepared in reaction and they are as the purposes of inhibiter.
Comprising the toxilic acid unit of modification and the multipolymer of other comonomers is known in principle.
EP-A 244584 discloses the toxilic acid unit that comprises modification and vinylbenzene or sulfonated phenylethylene, alkyl vinyl ether, C
2-C
6The multipolymer of alkene and (methyl) acrylamide.The toxilic acid unit of modification has the functional group that connects via spacer, and described examples of groups is-OH ,-OR ,-PO
3H
2,-OPO
3H
2,-COOH or preferred-SO
3H.
EP-A 1288232 and EP-A 1288228 disclose the multipolymer of the toxilic acid unit that comprises modification and other monomers such as acrylate, vinyl ether or alkene.The toxilic acid unit of modification is maleinamide and/or the maleimide that N-replaces.The N-substituting group is the heterogeneous ring compound that connects via spacer.
WO 99/29790 discloses the maleimide amine unit of N-replacement and the multipolymer of vinylbenzene or 1-octene.The maleimide amine unit is replaced by the piperazine unit that connects via spacer.
In conventional corrosion control technology, apply multiple different coating to the metallic surface usually.In the coil coating field, at first carry out pre-treatment usually, for example phosphorylation is handled, and applies undercoat at the top.On undercoat, can apply one or more layers inter coat or finishing coat.Using the corrosion control lacquer to carry out applying undercoat, inter coat and finishing coat usually under the situation of atomospheric corrosion control.
In modern corrosion control, the use of Chrome-free corrosion control system is more and more.In addition, require to simplify above-mentioned coating system.For this reason, the integration corrosion control coating that for example can use the integration corrosion control coating that makes up mutually down to the performance of major general's pre-treatment and undercoat in the situation of coil coating and make up mutually down to the performance of major general's undercoat and inter coat in the situation of atomospheric corrosion control, thus one deck coating rather than two layers of coatings only applied.
The purpose of this invention is to provide the improved inhibiter that is particularly useful for described application.These inhibiter especially should be able to be used for producing the integration corrosion control coating.
Therefore had been found that the multipolymer of forming by following structural unit:
(I) structural unit (I) of at least a derivative from monoethylenically unsaturated dicarboxylic acid of 1-99mol% is selected from structural unit (Ia), (Ib), (Ic), (Id), (Ie) and (If):
(II) 99-1mol% at least a other from monoene belong to unsaturated monomer non-(I) structural unit (II) and
(III) the other structural unit (III) of at least a ethylenically unsaturated monomer from other non-(I) and non-(II) of Ren Xuan 0-30mol%,
Wherein monomeric amount has following definition based on the total amount and the abbreviation of all monomeric units in this multipolymer in each case:
R
1: have (n+1) valency alkyl of 1-40 carbon atom, wherein non-adjacent carbon atom can also be substituted by O and/or N,
R
2, R
3: be H, methyl, C independently of one another
2-C
6Alkyl, perhaps R
2And R
3Be trimethylene or tetramethylene together,
R
4: H, C
1-C
10Alkyl or-(R
1-X
1 n),
M:H or positively charged ion,
X wherein
1For being selected from-SR
5,-CSNR
5 2Or-functional group and the R of CN
5For H or have the alkyl of 1-6 carbon atom, and n is 1,2 or 3.
In a second aspect of the present invention, found a kind of method by this analog copolymer of prepared in reaction that is similar to polymkeric substance.
In a third aspect of the present invention, found the purposes of this multipolymer as inhibiter.
The following describes details of the present invention.
According to the present invention, this multipolymer is made up of at least a structural unit of 1-99mol% (I), at least a structural unit of 99-1mol% (II) and optional 0-30mol% structural unit (III), and wherein quantitative value is in each case based on the total amount of mixing all structural units in this multipolymer by copolymerization.Except structural unit (I), (II) with (III), there are not other structural units to exist.
Structural unit (I)
Structural unit (I) is the derivative of monoethylenically unsaturated dicarboxylic acid, is selected from structural unit (Ia), (Ib), (Ic), (Id), (Ie) and (If):
In these structural units, X
1For being selected from-SR
5,-CSNR
5 2Or-functional group of CN.R wherein
5For H or have the alkyl of 1-6 carbon atom, especially have the linearity or the branched-alkyl of 1-6 carbon atom.This for example can be methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 1-amyl group or 1-hexyl.Preferred R
5Be H or methyl, more preferably H.Preferably-CSNR
2Or-CN, more preferably-CSNH
2When a structural unit has the X of two or more functional groups
1The time, described radicals X
1Can be identical or different, the X of functional group
1Number n be generally 1,2 or 3, preferred 1 or 2, more preferably 1.
Radicals R
1For with the X of functional group
1Be connected in the spacer of the rest part of structural unit (I).This moment R
1For having (n+1) valency alkyl of 1-40 carbon atom, wherein non-adjacent carbon atom can also be substituted by O and/or N.Described group is preferably has 1-20 carbon atom, more preferably 2-10 carbon atom, the very preferably alkyl of 2-6 carbon atom.This alkyl can be a branching or preferred linear.Described group is preferably 1, ω-functional group.
At divalent linker R
1Situation under, described group can be preferably has 1-20, the linearity 1 of preferred 2-6 carbon atom, ω-alkylidene group.More preferably described group is ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene.Preferably they can be the groups that contains the O atom in addition, for example-and CH
2-CH
2-O-CH
2-CH
2-, or general formula-CH
2-CH
2-[O-CH
2-CH
2-]
m-poly-alkoxyl group, wherein m is the natural number of 2-13.
If radicals R
1Two or more functional groups to be coupled together, then in principle two or more functional groups can key on terminal carbon.Yet, this moment R
1Preferably in carbon skeleton, have one or more branch points and each X of functional group
1Be connected in endways on each side chain.Branch point can be a carbon atom, or the preferred nitrogen atom.This class linking group R
1An example comprise-CH
2-CH
2-N (CH
2-)-
2
R
2And R
3Be equipped with is H, methyl or C certainly independently
2-C
6Alkyl, especially linear alkyl chain such as ethyl, 1-propyl group, 1-butyl, 1-amyl group or 1-hexyl.In addition, R
2And R
3Can also interconnect; This moment, the gained group especially can be trimethylene or tetramethylene.Preferred R
2And R
3Be H or methyl, more preferably R independently of one another
2And R
3H respectively does for oneself.
R
4Be H or C
1-C
6Alkyl or be group-R
1-X
1 n, R wherein
1And X
1 nAs defined above.R
4Be preferably the group that is selected from H, methyl or ethyl, preferred H or methyl, very preferably H.
M is H or positively charged ion, preferred monovalent cation.The example of this cationoid especially comprises alkali metal cation such as Li
+, Na
+Or K
+In addition, it especially can be NH
4 +And organic ammonium salt.
Organic ammonium salt can be primary, the salt of the second month in a season or tertiary amine.Organic group in such amine can be alkyl, aralkyl, aryl or alkaryl.They are preferably linearity or branched-alkyl.They can additionally contain other functional groups.Such functional group is preferably OH group and/or ether.Amine can also be by ethoxylation.The example of suitable amine comprises the C of linearity, ring-type and/or branching
1-C
8Single-, two-and trialkylamine, the C of linearity or branching
1-C
8Single-, two-or trialkanolamine, especially single-, two-or trialkanolamine, the C of linearity or branching
1-C
8Single-, two-or the linearity of trialkanolamine or the C of branching
1-C
8Alkyl oxide, oligomeric amine and polyamine such as diethylenetriamine.Amine can also be heterocyclic amine, as morpholine, piperazine, imidazoles, pyrazoles, triazole, tetrazolium, piperidines.Particularly advantageous is to use those heterocycles with corrosion inhibition.Example comprises benzotriazole and/or tolyl-triazole.
Be understood that and in a kind of multipolymer, can have two or more different structural units (Ia)-(If).Preferably, exist the structural unit (Ia) contain acid amides and/or imide group, (Ib) and (Ic) or existence contain the structural unit (Id) of ester group and (Ie).
The structural unit of a kind (Ia)-(If) can have the identical X of functional group in each case
1Perhaps radicals X
1Can be different sorts.Especially can be used in combination CSNH mutually
2With the CN group.
All structural units (I) amount together is preferably 10-90mol%, more preferably 20-80mol%, and 30-70mol% very preferably, 40-60mol% for example is in each case based on the total amount of mixing all structural units in the multipolymer by copolymerization.
Structural unit (II)
Structural unit (II) belongs to non-(I) structural unit (II) of unsaturated monomer for one or more from monoene.
These can be that any required monoene belongs to unsaturated monomer in principle, condition be they can with structural unit (I) based on monoethylenically unsaturated dicarboxylic acid and/or its derivative copolymerization.Those of skill in the art suitably select according to the desired properties of polymkeric substance.
Monoene belongs to unsaturated monomer (II) and can belong to unsaturated hydrocarbons (IIa) and/or use the X of functional group at least a monoene
2The monoene of modification belongs to unsaturated hydrocarbons (IIb).
(IIa)
(IIa) can comprise that in principle all have the hydrocarbon of ethylenically unsaturated group.These can be the aliphatic hydrocrbon (alkene) and/or the clicyclic hydrocarbon (cycloolefin) of linearity or branching.They can also be hydrocarbon, the especially vinyl aromatic compounds that also has aromatic group except ethylenically unsaturated group.Preferred they be wherein double bond position in the ethylenically unsaturated hydrocarbons of α position.Usually, at least 80% used monomer (IIa) should have two keys in the α position.
Term " hydrocarbon " also is intended to comprise propylene or has the not branching of ethylenically unsaturated group or the C of preferred branched
4-C
10The oligopolymer of alkene.The number-average molecular weight M that used oligopolymer has usually
nBe no more than 2300g/mol.Preferred M
nBe 300-1300g/mol, more preferably 400-1200g/mol.The oligopolymer of preferred iso-butylene, it can also be chosen wantonly and comprise other C
3-C
10Olefin comonomer.This quasi-oligomer based on iso-butylene is called " polyisobutene " hereinafter according to common usage.Used polyisobutene preferably should have at least 70%, more preferably α-double bond content of at least 80%.This class polyisobutene that is also referred to as reactive polyisobutene is known to those of skill in the art and can be commercial.
Except described oligopolymer, the monoene with 6-30 carbon atom belongs to unsaturated hydrocarbons and is particularly suited for implementing the present invention.The example of such hydrocarbon comprises hexene, heptene, octene, nonene, decene, undecylene, dodecylene, tetradecene, cetene, vaccenic acid, eicosane, docosane, preferred in each case 1-alkene or vinylbenzene.
The preferred use has 9-27 carbon atom, more preferably 12-24 carbon atom, and for example the monoene of 18-24 carbon atom belongs to unsaturated hydrocarbons.Be understood that the mixture that can also use different hydrocarbon.These mixtures can also be the cuts of different hydrocarbon, and example is industrial C
20-24Mixture.
Used monoene belongs to unsaturated hydrocarbons and is preferably linear or substantially linear at least." substantially linear " is intended to expression if there is any side group, and then they only are methyl or ethyl, preferably only are methyl.
Also specially suitable is described oligopolymer, preferred polyisobutene.Surprising is especially can improve processing characteristics in the Aquo System by this measure.Yet, preferably oligopolymer is not used as unique monomer, but mixes use with other monomers (IIa).Have been found that suitable to be oligomer be no more than 60mol% with respect to the summation of all monomers (II).If exist, the amount of oligopolymer is generally 1-60mol%, preferred 10-55mol%, more preferably 20-50mol%.
(IIb)
Hydrocarbon (IIb) is used the X of functional group
2The monoene of modification belongs to unsaturated hydrocarbons, can be in principle any have ethylenically unsaturated group and wherein one or more H atoms of this hydrocarbon by the X of functional group
2The alternate hydrocarbon.
These monomers can be alkene, cycloolefin or the alkene that contains aromatic group.Preferred wherein double bond position is in the ethylenically unsaturated hydrocarbons of α position.Monomer (IIb) has 3-30 carbon atom usually, preferred 6-24 carbon atom, more preferably 8-18 carbon atom.They have an X of functional group usually
2Monomer (IIb) is preferably the linearity with 3-30 carbon atom or the α-undersaturated-omega-functionalized alkene of substantially linear, and/or the vinylbenzene that replaces of 4-.
The X of functional group
2Can advantageously improve the performance of multipolymer, as the solvability in some preparaton and to the adhesion on some surface.The X of functional group
2Be preferably at least a following the group :-OR that is selected from
7,-SR
7,-NR
7 2,-NH (C=O) R
7, COOR
7The R of ,-(C=O)
7,-COCH
2COOR
7,-(C=NR
7) R
7,-(C=N-NR
7 2) R
7,-(C=N-NR
7-(C=O)-NR
7 2) R
7,-(C=N-OR
7) R
7,-O-(C=O) NR
7,-NR
7(C=O) NR
7 2,-NR
7(C=NR
7) NR
7,-CSNR
7 2,-CN ,-PO
2R
7 2,-PO
3R
7 2,-OPO
3R
7 2,-SO
3R
7Or-Si (OR
8)
3, the R here
7Be H in each case, positively charged ion, preferred monovalent cation, or have the alkyl of 1-10 carbon atom, preferably C
1-C
6Alkyl.R
8Be C
1-C
6Alkyl.More preferably X
2For-COOH.
The example of proper monomer (IIb) comprises C
4-C
20(α, ω)-vinyl carboxylic acid, as vinylacetic acid or 10-undecylene formic acid, C
2-C
20(α, ω)-vinyl phosphonate such as vinyl phosphonate, its monoesters or diester or salt, C
3-C
20Vinyl nitrile such as vinyl cyanide, allyl cyanide, 1-butylene nitrile, 2-methyl-3-crotononitrile, 2-methyl-2-butene nitrile, 1-, 2-, 3-or allyl acetonitrile or 1-hexene nitrile, the vinylbenzene that 4-replaces is as 4-hydroxy styrenes or 4-carboxyl styrene.Be understood that the mixture that can also use two or more different monomers (c1b ').Preferably (c1b ') be 10-undecylene formic acid.
(IIc)
As structural unit (II), demonomerization (IIa) and (II) b) can also use or replace monomer (IIa) and (IIb) use other monoene to belong to unsaturated monomer (IIc) outward.
Suitable monomers (IIc) comprises (methyl) acrylic acid series compound as (methyl) vinylformic acid, and (methyl) acrylate or (methyl) acrylamide especially have straight chain or branching C
1-C
20Alkyl, preferred C
2-C
10(methyl) acrylate of alkyl is as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate or (methyl) 2-ethylhexyl acrylate.They can also be to have (methyl) acrylate, particularly OH-functional monomer of extra functional group as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester or (methyl) vinylformic acid 4-hydroxybutyl ester.The example of other monomers (IIc) comprises alkyl vinyl ether, as 1,4-hydroxymethyl-cyclohexane mono vinyl ether, glycol monomethyl vinyl ether, diglycol monotertiary vinyl ether, hydroxybutyl vinyl ether, methylvinylether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl, octadecyl Vinyl Ether or tert-Butyl vinyl ether, or vinyl ester such as vinyl-acetic ester or propionate.
The amount of structural unit (II) is preferably 10-90mol%, more preferably 20-80mol%, and 30-70mol% very preferably, 40-60mol% for example is in each case based on the total amount of mixing all structural units in the multipolymer by copolymerization.
(IId)
Structural unit (II) can additionally be to come the not deutero-monoethylenically unsaturated dicarboxylic acid of self-drifting (I ' g) and/or (I ' h) and/or the structural unit (IId) of its acid anhydrides:
R wherein
2, R
3With M as defined above.
(IIe)
Structural unit (II) can additionally be structural unit (IIe), and it is corresponding to the definition of structural unit (Ia)-(If), but wherein replaces the X of functional group
1, described group is non-X
1The X of functional group
3The X of functional group
3Especially can be selected from following a kind of :-OR
7,-NR
7 2,-NH (C=O) R
7, COOR
7The R of ,-(C=O)
7,-COCH
2COOR
7,-(C=NR
7) R
7,-(C=N-NR
7 2) R
7,-(C=N-NR
7-(C=O)-NR
7 2) R
7,-(C=N-OR
7) R
7,-O-(C=O) NR
7,-NR
7(C=O) NR
7 2,-NR
7(C=NR
7) NR
7,-PO
2R
7 2,-PO
3R
7 2,-OPO
3R
7 2,-SO
3R
7Or-Si (OR
8)
3, R wherein
7And R
8As defined above.Preferred extra functional group here is OH, SO
3H or PO
3H.
Structural unit (II) is preferably monomer (IIa) and/or (IIb), more preferably monomer (IIa) or (IIa) and the mixture of other monomers (II).Preferred monomers in mixture (IIb).If there is a mixture, then the amount of monomer (IIa) preferably is 40mol% at least with respect to the summation of all monomers (II).Also there is (IId) class monomer usually in the preparation method that depends on polymkeric substance.
Structural unit (III)
Multipolymer of the present invention can further comprise 0-30mol%, preferred 0-10mol%, more preferably 0-5mol%, very preferably 0-3mol% be different from (I) and (II) but can with (I) and (II) other ethylenically unsaturated monomers of copolymerization as the formation unit.Can use this class monomer in case of necessity, with the performance of fine setting multipolymer.Very particularly preferably there is not monomer (III).
The example of monomer (III) comprises the compound that comprises two or more two keys.These compounds can be for having the hydro carbons of conjugated double bond, as divinyl or isoprene.In addition, they can be to have the cross-linking monomer that two or more separate ethylenical unsaturated double bonds.Yet multipolymer of the present invention should be too much not crosslinked.If there is cross-linking monomer, then its amount should not surpass 5mol% usually with respect to all monomeric summations, preferred 3mol%, more preferably 2mol%.
The preparation of multipolymer
The preparation of multipolymer of the present invention can preferably be undertaken by the reaction that is similar to polymkeric substance.
Under the situation of this method, the multipolymer of the unmodified monoethylenically unsaturated dicarboxylic acid of preparation and/or its salt and monomer (II) and optional (III) in the first step.Replace this dicarboxylic acid, can also use the reactive derivatives of dicarboxylic acid, example is corresponding dicarbapentaborane halogen or especially dicarboxylic anhydride.Preferably can use the acid anhydrides of cis dicarboxylic acid, preferred especially maleic anhydride.Multipolymer as raw material has structural unit (IId1) and/or preferred (IId2).This analog copolymer can also be commercial.
Preparation as the unmodified polymer of raw material especially can be undertaken by the free radical addition polymerization.Be known to those of skill in the art on the implementation principle of free radical addition polymerization.Polymerization preferably uses the thermolysis polymerization starter to carry out, but can also the photochemistry mode carry out certainly.
As being used for the polymeric solvent, preferably can use aprotic solvent such as toluene, dimethylbenzene, aliphatic hydrocrbon, paraffinic hydrocarbons, gasoline or ketone.The long-chain monoene that has higher when use belongs to unsaturated hydrocarbon monomer, when especially boiling point is greater than about 150 ℃ those, can also solvent-freely operate.This moment, unsaturated hydrocarbons itself was as solvent.
Use the radical polymerization of thermal initiator can be, preferred 80-200 ℃, more preferably 100-180 ℃, especially carry out under 130-170 ℃ at 60-250 ℃.Amount of initiator is 0.1-10 weight % with respect to amount of monomer, preferred 0.2-5 weight %, more preferably 0.5-2 weight %.Usually the amount of about 1 weight % is favourable.Polymerization time is generally 1-12 hour, and preferred 2-10 hour, more preferably 4-8 hour.This multipolymer can or directly obtain with solvent-free form by known method of those of skill in the art and separated from solvent.
After unmodified multipolymer feedstock production was come out, the reaction that can be similar to polymkeric substance made the dicarboxylic acid units of copolymerization, preferred corresponding dicarboxylic anhydride unit, more preferably maleic anhydride unit and general formula HO-R
1-X
1 n(1) functional alcohol and/or general formula HR
4N-R
1-X
1 n(2) functional amine's reaction, wherein R
1, R
4, n and X
1As defined above.Preferred these be wherein n=1 1, omega-functionalized compound.
The example of compound (1) and (2) comprises general formula H
2N-(CH
2-)
kLinear 1-amino-ω-itrile group paraffinic hydrocarbons of-CN is as H
2N-(CH
2-)
6-CN or H
2N-(CH
2-)
4-CN, wherein k is 1-20, preferred 2-6.Other examples comprise HO-(CH
2-)
k-CN, H
2N-(CH
2-)
k-CSNH
2, HO-(CH
2-)
k-CSNH
2, HO-CH for example
2-CH
2-CSNH
2, HO-(CH
2-)
k-SH, for example HO-CH
2-CH
2-SH or H
2N-(CH
2-)
k-SH.
This reaction can be carried out by body, or preferably carries out in suitable aprotic solvent.The example of suitable aprotic solvent especially comprises polar aprotic solvent such as acetone, methyl ethyl ketone (MEK), two alkane or THF and suitable words non-polar hydrocarbon such as toluene or aliphatic hydrocrbon.
For this reaction, unmodified multipolymer for example can be introduced in the solvent, can add required functional alcohol HO-R by aequum then
1-X
1 n(1) and/or required functional amine HR
2N-R
1-X
1 n(2).The functionalized reagent can suitably be dissolved in the suitable solvent in advance.Derivatize preferably carries out under heating.Have been found that suitable within the scope of the present invention temperature is 30-150 ℃, preferred 40-130 ℃, more preferably 60-120 ℃.Have been found that the suitable reaction times is 2-25 hour.When under 100 ℃ temperature at the most, using primary amine, preferentially obtain corresponding acid amides, and under higher temperature, also can form imide gradually.Imido formation has accounted for leading under 130-140 ℃.Preferably should avoid the formation of imide structure.
Reagent (1) and (2) consumption in functionalized are determined by required degree of functionalization.Have been found that appropriate vol is 0.5-1.5 equivalent/dicarboxylic acid units, preferred 0.6-1.2 equivalent/dicarboxylic acid units, more preferably 0.8-1.1 equivalent/dicarboxylic acid units, very preferably about 1 equivalent/dicarboxylic acid units.
When the multipolymer of modification still had unreacted anhydride group, these groups can be opened in second step in hydrolysis.This is for example by adding water and alkali in the organic solution, then vigorous stirring and carrying out.For this reason, have been found that suitable temperature is for being no more than 100 ℃, for example 80-100 ℃.
Certainly can also use two or more functional alcohol HO-R
1-X
1 n(1) and/or ammonia and/or functional amine HR
2N-R
1-X
1 n(2) mixture.Same possible be wherein at first to carry out with the reaction of functional alcohol or amine and after reaction, add other functional amines or pure reaction sequence respectively.
The organic solution of gained modified copolymer can be directly used in preparation can organic cross-linked formulations.Yet, be understood that this polymkeric substance can also separate by the known method of those of skill in the art from these solution.
In order to mix in the aqueous formulation, can suitably water be added in this solution, and by known method of those of skill in the art such as fractionation by distillation organic solvent.
The gained multipolymer can also be neutralized wholly or in part.The pH of this copolymer solution should be at least 6 usually, and preferably at least 7, to guarantee in water, having enough solvabilities or dispersiveness.The example that is suitable for neutral alkali comprises ammonia, basic metal and alkaline earth metal hydroxides, zinc oxide, the C of linearity, ring-type and/or branching
1-C
8Single-, two-and trialkylamine, the C of linearity or branching
1-C
8Single-, two-or trialkanolamine, especially single-, two-or trialkanolamine, the C of linearity or branching
1-C
8Single-, two-or the linearity of trialkanolamine or the C of branching
1-C
8Alkyl oxide, oligomeric amine and polyamine such as diethylenetriamine.This alkali can use or advantageously in fact use in the hydrolytic process of anhydride group subsequently.
The molecular weight M of this multipolymer
wSelect according to required end-use by those of skill in the art.Have been found that suitable M
wBe 1000-100000g/mol, preferred 1500-50000g/mol, more preferably 2000-20000g/mol, very preferably 3000-15000g/mol, for example 8000-14000g/mol.
Be similar to two or more structural units (Ia)-(Ic) that stock polymer that polymkeric substance functionalised has mutual arrangement usually, (Id) and (Ie), the not functionalized group of (If) and suitable words (I ' g) and (I ' h).The ratio of structural unit is by the ratio and the reaction conditions decision of the character of used difunctional's compound (1) and/or (2), selected polymkeric substance and difunctional's compound.If R
4Be H, then only can form the imide unit certainly, simultaneously, higher temperature of reaction helps the formation of imide group usually.
In another route of synthesis, at first can be by undersaturated unmodified dicarboxylic acid of olefinic or dicarboxylic acid derivatives in the synthesis step that separates, preferred dicarboxylic acid anhydride, more preferably cis dicarboxylic anhydride and functional alcohol HO-R
1-X
1 n(1) and/or functional amine HR
4N-R
1-X
1 n(2) the monomer dicarboxylic acid of synthetic derivatize.Then can be with the monomer of these derivatizes with other above-mentioned monomer polymerizations.
The multipolymer that contains the thioamides group also can contain the polymkeric substance of itrile group and make itrile group with known mode and H in principle after polymerization by preparation at first
2The S reaction obtains the thioamides group and prepares.With H
2The reaction of S can advantageously be carried out in the presence of alkali.For example can use pressure exerting device and carry out as the methyl alcohol of solvent.Transforming degree for example can by
13C NMR spectrum is by comparing CN and CSNH
2The intensity of signal and determining.
The purposes of polymkeric substance
Polymkeric substance of the present invention can be used for any of unusual wide region purpose; For example as inhibiter, scale inhibitor, adhesion promotor or dispersing auxiliary.
They especially are suitable as inhibiter.Thus, this polymer properties especially can be passed through structural unit (I) and (II) and the property quality and quantity of suitable (III) and each optimizing application is regulated.For example can synthesize and organic solvent or water and/or water-containing solvent compatible polymers.For Aquo System, advantageously the ratio of structural unit (I) is not less than 40mol%.In addition, can use the monomer of hydrophilic modifying such as hydroxy styrenes or styrene sulfonic acid as monomer (IIb) for this reason.
Multipolymer of the present invention for example can be used as inhibiter or scale inhibitor in Aquo System such as chilled(cooling) water return (CWR).
They especially are fit to produce the preparaton that is used for corrosion control lacquer and coating.Thus, related preparaton can be to be used for the preparaton of atomospheric corrosion control or to be used for the preparaton that the coiled material coating is used.For these purposes, they are prepared with suitable binder systems for use, pigment and/or filler and suitable words solvent and other auxiliary agents.Thus, have been found that appropriate vol is 0.1-40 weight %, preferred 0.2-20 weight %, more preferably 0.5-10 weight % is in each case based on the amount of all components in the preparaton.
Described preparaton can put on any required metallic surface; Yet they especially are fit to protection iron, steel, zinc, zinc alloy, aluminum or aluminum alloy.
The example that is fit to the binder systems for use of coiled material coating application is based on the thermoset system of Resins, epoxy, urethane and acrylate dispersoid, and it normally solidifies under the temperature more than 100 ℃ in the temperature that raises.But can use the system of photochemical crosslinking in addition.Preparaton can put on the metal coiled material by for example dip-coating or roller coat, solidifies by heating or radiation then.
The example that is suitable for the binder systems for use of atomospheric corrosion control is to solidify under atmospheric condition and based on the binder systems for use of polyacrylic ester, copolymer in cinnamic acrylic ester, vinylbenzene-alkadiene hydrocarbon polymer, urethane or Synolac.
Preparaton can put on metallic surface, for example steel structure body surface by for example brushing or spraying.The coating that applies contacts with atmosphere then and solidifies.
The following example is used to illustrate the present invention.
Synthesizing of A part-used multipolymer
Synthesizing of part i-raw material: multipolymer with anhydride group
Copolymer A
MAn/C
12Alkene/C
20-24The multipolymer of alkene (mol ratio 1/0.6/0.4)
In the 1500L pressurized reactor that is having anchor stirrer, temperature regulator and nitrogen inlet tube under 60 ℃, pump into 36.96kg C
20-24Alkene also sucks positive 12 carbon of 31.48kg-1-alkene.This initial charge is heated to 150 ℃.Be metered into charging of forming by the 1.03kg di-t-butyl peroxide 1 and the charging of forming by 30.57kg fusion maleic anhydride 2 then through 6 hours.After charging 1 and 2 finishes, this batch of material was stirred 2 hours down at 150 ℃.Under the 150-200 millibar, remove the acetone and the trimethyl carbinol then by distillation.
Multipolymer B
MAn/C
12The multipolymer of alkene/polyisobutene 1000 (mol ratio 1/0.8/0.2)
In having the 2L pilot scale stirrer of anchor stirrer and internal thermometer, with 600.0g (0.6mol) M
nHighly reactive polyisobutenes (alpha-olefin content＞80%) (Glissopal for 1000g/mol
1000, BASF) and 322.5g (1.92mol) C
12Alkene is heated to 150 ℃ under stirring and nitrogen protection.Be metered into through 6 hours then by the 294.0g maleic anhydride (80 ℃, the 3.0mol) charging 1 of Zu Chenging and by 13.0g di-t-butyl peroxide (is 1% based on monomer) and 80.6g (0.48mol) C
12The charging 2 that alkene is formed.After charging 1 and 2 reinforced end, with this batch of material 150 ℃ of following restir 2 hours.Obtain the yellow solid polymkeric substance.
Part ii-multipolymer functionalized
General test explanation II-1
In having the 2L pilot scale stirrer of anchor stirrer and internal thermometer, be added in specific required maleic anhydride-olefin copolymer A in the organic solvent or B and should at the beginning of expect and used nitrogen protection.Under y ℃, dripped the specific required hydroxyl of 1 equivalent-or amino-functional compounds (1) or (2) then through x hour.
Exchange of solvent:
After derivatize, can carry out the exchange of organic solvent and water.Product is mixed with water and alkali for this reason, reach desired level up to pH.Remove organic solvent by distillation under reduced pressure then.
General test explanation II-2:
In having the 2L pilot scale stirrer of anchor stirrer and internal thermometer, add the specific required hydroxyl of specific required maleic anhydride-olefin copolymer A or B and 1 equivalent-or amino-functional compounds (1) or (2) and should just expect with nitrogen protection and y ℃ of stirring x hour down.Then product is dissolved in the appropriate organic solvent.
After derivatize, can carry out the exchange of organic solvent and water as previously mentioned.
Used particular polymers, used hydroxyl-amino-functional compounds (I) or (II) and other details of the performance of the multipolymer of gained derivatize be summarized in the table 2.
The product of derivatize is separately by the NMR spectrum analysis.Bright OH in each case of described stave and/or NH
2Group and carboxyl functional group reaction.
Table 2: with the multipolymer of functionalized alcohol (1) or amine (2) derivatize
| Multipolymer number | Raw materials used | Explanation | Solvent | Alkali | Functional alcohol (I) or functional amine (II) | Mol ratio | Time [h] | Temperature [℃] | Solids content [weight %] | pH |
| Copolymer 1 | A | 2 | Two alkane/MEK and H 2The O exchange of solvent | DMEA to pH 8.7 | The hydroxyl thiopropionamide | 1∶1 | 4 | 100 | 25.1 | 8.7 |
| Multipolymer 2 | A | 2 | MEK and H 2The O exchange of solvent | DMEA to pH 8.7 | Mercaptoethanol | 1∶0.8 | 16 | 90 | 23.3 | 8.4 |
| Multipolymer 3 | B | 1 | MEK | - | Aminocapronitrile | 1∶1 | 3 | 66 | 48.2 | - |
| Multipolymer 4 | B | 2 | MEK | - | The hydroxyl thiopropionamide | 1∶1 | 3 | 105 | 47.7 | - |
| Multipolymer 5 | B | 2 | MEK and H 2The O exchange of solvent | DMEA to pH 8.2 | The hydroxyl thiopropionamide | 1∶1 | 3 | 105 | 19.5 | 8.2 |
| Multipolymer 6 | B | 2 | Two alkane/MEK | - | Mercaptoethanol | 1∶0.8 | 25 | 95-99 | 54.4 | - |
| Multipolymer 7 | B | 2 | Do not have, add H 2O/ DMEA and BG exchange of solvent | DMEA | (hydroxyethyl) amino dimethylene phosphonic acids four (triethyl ammonium) salt | 1∶1 | 4.5 | 103 | 20.5 | Do not survey |
DMEA: dimethylethanolamine, MEK: methyl ethyl ketone, BG: butyl glycol
B part-performance test
Use the underivatized of gained and the toxilic acid-olefin copolymer of derivatize to make a service test.
3 kinds of different coil coatings based on epoxide, acrylate and urethane are tested.
Basic components based on the coil coating (organic) of epoxy base material
The component that is used to produce the preparaton of integrating pretreatment coating is as follows:
| Component | Explanation | Amount [weight part] |
| Base-material with crosslinked group | Epoxy base material (molecular weight 1000g/mol, viscosity 13dPas/s and solids content 50%) based on dihydroxyphenyl propane | 26.9 |
| Filler | Hydrophilic fumed silica (Aerosil 200V，Degussa) | 0.16 |
| Finntalk M5 talcum | 2.9 | |
| Rutile type titanium 2310, white pigment | 10.8 | |
| Silicon-dioxide (the Shieldex of calcium ion modification ，GraceDivision) | 3.0 | |
| Zinc phosphate (Sicor ZP-BS-M，WaardalsKjemiskeFabriken) | 4.1 | |
| Black pigment (Sicomix Schwarz，BASF AG) | 1.0 | |
| Solvent | Butyl glycol | 5.0 |
In suitable stirred vessel, each component is mixed with described order and used dissolver pre-dispersed 10 minutes.The gained mixture transferred in the ball mill with cooling jacket and with the 1.8-2.2mmSAZ granulated glass sphere mix.Abrasive was ground 1 hour 30 minutes.Then abrasive is separated with granulated glass sphere.
Under agitation in abrasive, add the end capped hexamethylene diisocyanate (Desmodur of 5.9 weight parts with described order
VP LS 2253, Bayer AG) and the commercially available not stanniferous crosslinking catalyst (Borchi of 0.4 weight part
VP 0245, Borchers GmbH).
Basic components based on the coil coating (water-based) of acrylate base-material
Used cross-linkable binder is the amine stabilized acrylate water dispersion of negatively charged ion (solids content is 30 weight %), and it is formed by following main monomer: n-butylacrylate, vinylbenzene, vinylformic acid and methacrylic acid hydroxyl propyl diester.
In suitable stirred vessel, mix flow control agent, the 5.5 weight part melamine resin linking agent (Luwipal that 18.8 parts by weight of acrylic acid ester dispersions, 4.5 weight part dispersing additives, 1.5 weight parts have defoamer effect with described order
072, BASF AG), the hydrophilic pyrogenic silica of the 0.2 weight part (Aerosil of Degussa
200V), 3.5 weight part Finntalk M5 talcums, 12.9 weight part rutile type titaniums, 2310 white pigments, 8.0 parts by weight of acrylic acid ester dispersions, the 3.5 weight parts silicon-dioxide (Shieldex of Grace Division of calcium ion modification
), the 4.9 weight part zinc phosphates (Sicor of Waardals Kjemiske Fabriken
ZP-BS-M), the 1.2 weight part black pigment (Sicomix of BASF AG
Schwarz) also use pre-dispersed 10 minutes of dissolver.The gained mixture transferred in the ball mill with cooling jacket and with 1.8-2.2mm SAZ granulated glass sphere mix.Abrasive was ground 45 minutes.Then abrasive is separated with granulated glass sphere.
Under agitation in abrasive, sneak into 27 parts by weight of acrylic acid ester dispersions, 1.0 weight part defoamers, 3.2% end capped sulfonic acid, 1.5 weight part defoamers and 1.0 weight part flow control auxiliary agents with described order.
Basic components based on the coil coating (water-based) of urethane base-material
Used cross-linkable binder is based on the polyester glycol (M as soft section
nAbout 2000g/mol), 4,4 '-two (isocyanate group cyclohexyl) methane and contain the monomer of acidic-group and the polyurethane aqueous dispersion body of chainextender (solids content 44 weight %, acid number 25, M
nAbout 8000g/mol, M
wAbout 21000g/mol).
In suitable stirred vessel, mix flow control agent, the 5.5 weight part melamine resin linking agent (Luwipal that 18.8 weight part polyurethane dispersions, 4.5 weight part dispersing additives, 1.5 weight parts have defoamer effect by described order
072, BASF AG), the hydrophilic pyrogenic silica of the 0.2 weight part (Aerosil of Degussa
200V), 3.5 weight part Finntalk M5 talcums, 12.9 weight part rutile type titaniums, 2310 white pigments, 8.0 weight part polyurethane dispersions, the 3.5 weight parts silicon-dioxide (Shieldex of Grace Division of calcium ion modification
), the 4.9 weight part zinc phosphate (Sicor of WaardalsKiemiske Fabriken
ZP-BS-M), the 1.2 weight part black pigment (Sicomix of BASF AG
Schwarz) also use pre-dispersed 10 minutes of dissolver.The gained mixture transferred in the ball mill with cooling jacket and with 1.8-2.2mm SAZ granulated glass sphere mix.Abrasive was ground 45 minutes.Then abrasive is separated with granulated glass sphere.
Under agitation in abrasive, sneak into 27 weight part polyurethane dispersions, 1.0 weight part defoamers, 3.2% an acidic catalyst (end capped tosic acid, Nacure with described order
2500), 1.5 weight part defoamers and 1.0 weight part flow control auxiliary agents.
The adding of multipolymer of the present invention
The multipolymer (solid ingredient with respect to preparaton is calculated with solid copolymer) that in described coil coating, adds the above-mentioned derivatize of 5 weight % in each case.For this reason, use the above-mentioned solution of multipolymer in butyl glycol for organic coating based on epoxide; Use the described aqueous solution or emulsion for water-borne coatings based on acrylate or epoxide.
The coating of steel and aluminium sheet
Z type steel plate galvanized is used in the coating test, and (OEHDG 2, and Chemetall) (AA6016 Chemetall) carries out with aluminium sheet AlMgSi.These plates clean by currently known methods in advance.
Described coil coating uses the coating rod to apply, and it is that 185 ℃ and base material temperature are to solidify in 171 ℃ the through type moisture eliminator to obtain the coating that build is 6 μ m that wet-film thickness should make in circulating air temperature.
In order to contrast, also produce the coating that does not add multipolymer.
In order to test the corrosion mitigating effect of coating of the present invention, steel plate galvanized is carried out 10 all VDA[GermanAutomobile Industry Association] climate cycle test (VDA test panel 621-415, February nineteen eighty-two).
In this test (row diagram as follows), at first sample is exposed to salt-fog test 1 day (5%NaCl solution, 35 ℃), alternately be exposed to wet condition (40 ℃, 100% relative humidity) and drying conditions (22 ℃, 60% relative humidity) 3 times then.The drying conditions stage by 2 days is finished circulation.It is as shown below to circulate.
Carry out 10 these exposure cycle altogether one by one.
After corrosion exposes end, by visual assessment steel plate with the standard comparison of determining.Estimate the formation of corrosion products on the not impaired film surface and the underfilm corrosion at cut and edge and spread tendency.
Based on the comparative evaluation sample of the control sample that does not add the inhibition multipolymer.
Additionally by the corrosion mitigating effect of estimating steel plate according to the salt-fog test of DIN 50021.
On aluminium sheet, carry out acetic acid salt spray test ESS (DIN in June, 50021,88).This plate of visual assessment after corrosion exposes end.The infringement of in this test, estimating be on whole diaphragm area, occur annular layer from.
For all tests, delineation is filmed; This sees through the through steel layer of spelter coating under the situation of steel plate.
The assess sample by giving following scoring:
0 is the same with contrast corrosion-damaged
+ corrosion-damaged comparison is according to lacking
++ corrosion-damagedly significantly be less than contrast
-corrosion-damaged comparison is according to wanting many
Test-results is illustrated among the table 3-5.
Table 4: the corrosion test of using the multipolymer of the dicarboxylic acid units that contains derivatize
| Embodiment number | Used multipolymer | Monomer | Mol ratio | With following group functionalization's dicarboxylic acid units | Coating system | The steel plate galvanized climate cycle test | The test of aluminium sheet acetic acid salt spray |
| Embodiment 1 | Copolymer 1 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -CSNH 2 | Acrylate/two alkane/water | 0 | + |
| Embodiment 2 | Copolymer 1 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -CSNH 2 | PU/ two alkane/water | 0 | + |
| Embodiment 3 | Multipolymer 2 | MAn/C 12Alkene/C 20-24Alkene | 1/0.6/0.4 | -SH | Epoxy/MEK | + | + |
| Embodiment 4 | Multipolymer 3 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CN | Epoxy/MEK | + | + |
| Embodiment 5 | Multipolymer 4 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | Epoxy/MEK | + | + |
| Embodiment 6 | Multipolymer 5 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | Acrylate/two alkane/water | Not test | + |
| Embodiment 7 | Multipolymer 5 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -CSNH 2 | PU/ two alkane/water | 0 | + |
| Embodiment 8 | Multipolymer 6 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -SH | Epoxy/two alkane/water | + | + |
| Comparative Examples 1 | Multipolymer 7 | MAn/C 12Alkene/PIB 1000 | 1/0.8/0.2 | -PO 3H(2x) | Epoxy/MEK | + | - |
Embodiment shows the improvement of using the polymkeric substance of the present invention that contains the derivatize dicarboxylic acid units can obtain the corrosion control performance of coil coating.This improvement appears at two kinds of base materials at least, and one of aluminium or steel are gone up and all observed on two kinds of base materials usually.
In simultaneous test with phosphonyl group (2 of each dicarboxylic acid units) although the polymkeric substance of modification produces improvement under situation about applying on the galvanized steel, in fact on aluminium, cause the infringement.
Claims (18)
1. multipolymer of forming by following structural unit:
(I) structural unit (I) of at least a derivative from monoethylenically unsaturated dicarboxylic acid of 1-99mol% is selected from structural unit (Ia), (Ib), (Ic), (Id), (Ie) and (If):
(II) 99-1mol% at least a other from monoene belong to unsaturated monomer non-(I) structural unit (II) and
(III) the other structural unit (III) of at least a ethylenically unsaturated monomer from other non-(I) and non-(II) of Ren Xuan 0-30mol%,
Wherein monomeric amount has following definition based on the total amount and the abbreviation of all monomeric units in this multipolymer in each case:
R
1: have (n+1) valency alkyl of 1-40 carbon atom, wherein non-adjacent carbon atom can also be substituted by O and/or N,
R
2, R
3: be H, methyl, C independently of one another
2-C
6Alkyl, perhaps R
2And R
3Be trimethylene or tetramethylene together,
R
4: H, C
1-C
10Alkyl or-(R
1-X
1 n),
M:H or positively charged ion,
X wherein
1For being selected from-SR
5,-CSNR
5 2Or-functional group and the R of CN
5For H or have the alkyl of 1-6 carbon atom, and n is 1,2 or 3.
2. according to the multipolymer of claim 1, R wherein
2And R
3Be H.
3. according to the multipolymer of claim 1 or 2, X wherein
1For-CSNH
2
4. according to the multipolymer of claim 1 or 2, X wherein
1For-CN.
5. according to the multipolymer of claim 1 or 2, X wherein
1For-SH.
6. according to each multipolymer among the claim 1-5, comprise at least a monoene and belong to unsaturated hydrocarbons (IIa) and/or use the X of functional group
2The monoene of modification belongs to unsaturated hydrocarbons (IIb) as monomer (II).
7. according to the multipolymer of claim 6, wherein said monoene belongs to unsaturated hydrocarbons (IIa) and/or (IIb) has a 6-30 carbon atom.
8. according to the multipolymer of claim 6 or 7, further comprising based on the amount of all monomers (II) is at least a reactive polyisobutene of 1-60mol%.
9. according to each multipolymer among the claim 1-8, wherein the amount of structural unit (I) is that the amount of 30-70mol% and structural unit (II) is 70-30mol%.
10. one kind is used unmodified multipolymer as raw material and make this unmodified multipolymer and two functional alcohol HO-R
1-X
1 n(1) and/or two functional amine HR
4N-R
1-X
1 n(2) reaction obtains modified copolymer and prepares the method for multipolymer, and described unmodified multipolymer is made up of following structural unit: 1-99mol% from the structural unit (IId1) of unmodified monoethylenically unsaturated dicarboxylic acid, its salt or acid anhydrides and/or (IId2):
And 99-1mol% is at least a other belongs to non-(I) structural unit (II) of unsaturated monomer and the other structural unit (III) of at least a ethylenically unsaturated monomer from other non-(I) and non-(II) of the 0-30mol% that chooses wantonly from monoene, and wherein monomeric amount has following definition based on the total amount and the abbreviation of all monomeric units in this multipolymer in each case:
R
1: have (n+1) valency alkyl of 1-40 carbon atom, wherein non-adjacent carbon atom can also be substituted by O and/or N,
R
2, R
3: be H, methyl, C independently of one another
2-C
6Alkyl, perhaps R
2And R
3Be trimethylene or tetramethylene together,
R
4: H, C
1-C
10Alkyl or-(R
1-X
1 n),
M:H or positively charged ion,
X wherein
1For being selected from-SR
5,-CSNR
5 2Or-functional group and the R of CN
5For H or have the alkyl of 1-6 carbon atom, and n is 1,2 or 3.
11. according to the method for claim 10, the unmodified multipolymer that wherein uses dicarboxylic acid units wherein to exist with acid anhydrides unit (IId2) substantially.
12. according to the method for claim 10 or 11, wherein R
2And R
3Be H.
13. according to each method among the claim 10-12, wherein difunctional's compound (1) and/or (2) and dicarboxylic acid units and/or the unitary number of dicarboxylic anhydride are than being 0.5-1.5.
14. one kind can be by the multipolymer that obtains according to each method among the claim 10-13.
15. according to each multipolymer in claim 1-9 and 14 as the purposes of inhibiter.
16. according to the purposes of claim 15, wherein said inhibiter is as the additive of coil coating.
17. according to the purposes of claim 15, wherein said inhibiter is as the additive of atomospheric corrosion control with lacquer or coating proportional preparation.
18. according to each multipolymer in claim 1-9 and 14 as the purposes of the additive of Aquo System.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200510004292 DE102005004292A1 (en) | 2005-01-28 | 2005-01-28 | Method for applying corrosion protection layer on metallic surfaces comprises treating the surface with a formulation having binding agent, pigment and/or filler and corrosion protecting agent, which is a thioamide group containing compound |
| DE102005004292.9 | 2005-01-28 | ||
| DE102005061320.9 | 2005-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101155882A true CN101155882A (en) | 2008-04-02 |
Family
ID=36686449
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800035470A Expired - Fee Related CN101111573B (en) | 2005-01-28 | 2006-01-24 | Method for applying corrosion protection layers comprising thioamides to metallic surfaces |
| CNA2006800035273A Pending CN101111572A (en) | 2005-01-28 | 2006-01-24 | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| CN2006800035593A Expired - Fee Related CN101111574B (en) | 2005-01-28 | 2006-01-24 | Preparation and method for applying corrosion protection layers |
| CNA2006800034444A Pending CN101155882A (en) | 2005-01-28 | 2006-01-24 | Copolymer comprising monoethylenically unsaturated dicarboxylic acid derivatives |
| CN200680003468XA Expired - Fee Related CN101111571B (en) | 2005-01-28 | 2006-01-26 | Anti-corrosion coatings containing thioamide groups |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800035470A Expired - Fee Related CN101111573B (en) | 2005-01-28 | 2006-01-24 | Method for applying corrosion protection layers comprising thioamides to metallic surfaces |
| CNA2006800035273A Pending CN101111572A (en) | 2005-01-28 | 2006-01-24 | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| CN2006800035593A Expired - Fee Related CN101111574B (en) | 2005-01-28 | 2006-01-24 | Preparation and method for applying corrosion protection layers |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680003468XA Expired - Fee Related CN101111571B (en) | 2005-01-28 | 2006-01-26 | Anti-corrosion coatings containing thioamide groups |
Country Status (2)
| Country | Link |
|---|---|
| CN (5) | CN101111573B (en) |
| DE (1) | DE102005004292A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066358A (en) * | 2018-01-23 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of without phosphorus Polymer corrosion inhibitor and its preparation method and application |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392251A (en) * | 2011-11-17 | 2012-03-28 | 成都盛尔嘉科技有限公司 | Rust inhibitor |
| MX2015003231A (en) * | 2012-09-19 | 2015-07-14 | Akzo Nobel Coatings Int Bv | Aqueous coating compositions including the reaction product of maleic anhydride with an unsaturated compound and an amine. |
| CN103059234A (en) * | 2013-01-07 | 2013-04-24 | 辽宁工业大学 | Preparation method of black metal preservative |
| CN103725054A (en) * | 2013-11-25 | 2014-04-16 | 铜陵天河特种电磁线有限公司 | Amino resin wire enamel and preparation method thereof |
| CN103695931B (en) * | 2013-11-29 | 2016-08-24 | 明光市留香泵业有限公司 | A kind of Water-soluble metal short-term antirust liquid and preparation method thereof |
| CN105400262A (en) * | 2015-12-03 | 2016-03-16 | 巢湖诺信建材机械装备有限公司 | Isolation coating on temporary placing box made of alloy material |
| CN105440814A (en) * | 2015-12-23 | 2016-03-30 | 巢湖诺信建材机械装备有限公司 | Bottom layer protective coating on air cannon nozzle |
| CN105623606A (en) * | 2015-12-30 | 2016-06-01 | 安徽工业大学 | Oil and rust removing paste of copper and alloy material of copper |
| CN106047113A (en) * | 2016-07-27 | 2016-10-26 | 苏州明轩地坪涂料有限公司 | Efficient corrosion-resistant coating |
| CN113122031A (en) * | 2019-12-31 | 2021-07-16 | 江苏苏博特新材料股份有限公司 | In-situ polymerization type metal corrosion inhibitor and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2280578A (en) * | 1938-09-15 | 1942-04-21 | Du Pont | Amides of aliphatic polycarbothionic acids and their preparation |
| GB996489A (en) * | 1961-06-01 | 1965-06-30 | Ethyl Corp | Novel hydroxy thio benzamides |
| US3687908A (en) * | 1971-02-02 | 1972-08-29 | Us Air Force | Polymers containing nitrile and thioamide groups and their preparation |
| US5470908A (en) * | 1993-10-28 | 1995-11-28 | The Dow Chemical Company | Water-based acrylic coating compositions |
| JP4568386B2 (en) * | 1997-05-14 | 2010-10-27 | 日本ペイント株式会社 | Rust prevention coating agent and rust prevention treatment method |
-
2005
- 2005-01-28 DE DE200510004292 patent/DE102005004292A1/en not_active Withdrawn
-
2006
- 2006-01-24 CN CN2006800035470A patent/CN101111573B/en not_active Expired - Fee Related
- 2006-01-24 CN CNA2006800035273A patent/CN101111572A/en active Pending
- 2006-01-24 CN CN2006800035593A patent/CN101111574B/en not_active Expired - Fee Related
- 2006-01-24 CN CNA2006800034444A patent/CN101155882A/en active Pending
- 2006-01-26 CN CN200680003468XA patent/CN101111571B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066358A (en) * | 2018-01-23 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of without phosphorus Polymer corrosion inhibitor and its preparation method and application |
| CN110066358B (en) * | 2018-01-23 | 2022-09-27 | 中国石油化工股份有限公司 | Phosphorus-free polymer corrosion inhibitor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005004292A1 (en) | 2006-08-03 |
| CN101111571B (en) | 2011-07-06 |
| CN101111573A (en) | 2008-01-23 |
| CN101111574B (en) | 2010-06-16 |
| CN101111573B (en) | 2012-03-28 |
| CN101111571A (en) | 2008-01-23 |
| CN101111572A (en) | 2008-01-23 |
| CN101111574A (en) | 2008-01-23 |
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