CN1063752C - 丙烯酸酯基亚磷酸亚铜盐化合物 - Google Patents
丙烯酸酯基亚磷酸亚铜盐化合物 Download PDFInfo
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- CN1063752C CN1063752C CN96102548A CN96102548A CN1063752C CN 1063752 C CN1063752 C CN 1063752C CN 96102548 A CN96102548 A CN 96102548A CN 96102548 A CN96102548 A CN 96102548A CN 1063752 C CN1063752 C CN 1063752C
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- 229920000642 polymer Polymers 0.000 title abstract description 21
- 150000002902 organometallic compounds Chemical class 0.000 title 1
- -1 salt compound Chemical class 0.000 claims description 59
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- 125000001544 thienyl group Chemical group 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 50
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- 230000008901 benefit Effects 0.000 description 6
- PNNJYDODNCALKD-UHFFFAOYSA-M benzenethiolate;copper(1+) Chemical compound [Cu+].[S-]C1=CC=CC=C1 PNNJYDODNCALKD-UHFFFAOYSA-M 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
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- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- WURGXGVFSMYFCG-UHFFFAOYSA-N dichlofluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1 WURGXGVFSMYFCG-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical class CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- AFGACPRTZOCNIW-UHFFFAOYSA-N ethenylsulfanylethane Chemical compound CCSC=C AFGACPRTZOCNIW-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AWYFNIZYMPNGAI-UHFFFAOYSA-L ethylenebis(dithiocarbamate) Chemical compound [S-]C(=S)NCCNC([S-])=S AWYFNIZYMPNGAI-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- HDHLIWCXDDZUFH-UHFFFAOYSA-N irgarol 1051 Chemical compound CC(C)(C)NC1=NC(SC)=NC(NC2CC2)=N1 HDHLIWCXDDZUFH-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- LBBIZPKEHXAXHI-UHFFFAOYSA-N isocyano thiocyanate Chemical compound [C-]#[N+]SC#N LBBIZPKEHXAXHI-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 description 1
- 229920000940 maneb Polymers 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- IZXGMKHVTNJFAA-UHFFFAOYSA-N n-methyl-n-phenylprop-2-enamide Chemical compound C=CC(=O)N(C)C1=CC=CC=C1 IZXGMKHVTNJFAA-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- KGMXPXPXPAAUMD-UHFFFAOYSA-N propane;dihydrochloride Chemical compound Cl.Cl.CCC KGMXPXPXPAAUMD-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WJSXSXUHWBSPEP-UHFFFAOYSA-N pyridine;triphenylborane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 WJSXSXUHWBSPEP-UHFFFAOYSA-N 0.000 description 1
- PFSKLZABYDOTKP-UHFFFAOYSA-N pyridine;zinc Chemical compound [Zn].C1=CC=NC=C1 PFSKLZABYDOTKP-UHFFFAOYSA-N 0.000 description 1
- 229960002026 pyrithione Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- TXHPORRYUKITDP-UHFFFAOYSA-N sulfamoylsulfamic acid Chemical compound NS(=O)(=O)NS(O)(=O)=O TXHPORRYUKITDP-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 125000005000 thioaryl group Chemical group 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1415—Compounds containing the structure P-O-acyl, P-O-heteroatom, P-O-CN
- C07F9/1417—Compounds containing the structure P-O-C(=X)- (X = O, S, Se)
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
-
- 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
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本申请公开了如下通式表示的化合物:
式中X是Cl、SCN或苯硫基,且当X是Cl时,m=1;当X是SCN时,m=2;当X是苯硫基时,m=3。该通式的化合物或单体可与一种或多种已知的单体聚合成聚合物。这种聚合物可用作涂料中的粘合剂,以制造船用防污涂料组合物。也公开了一种防止表面污垢的方法。
Description
本发明涉及新颖的化合物,这些化合物在船用防污涂料组合物中特别有用。
几千年来,船舶和船用结构上的船底结垢一直是个悬而未决的问题。最近,这个问题已主要通过使用某些含对海洋生物体有毒的杀生物剂的涂料加以解决。当这些常规涂料处于海水中时会从涂料中渗出杀生物剂。
然而,这种涂料体系不能提供所需的毒物恒定释放,而且它在使用中不能被很好地腐蚀掉,这是因为从涂膜内部选择萃取可溶于水的组份并渗出毒物的结果。在涂膜(胶松香)渗走可溶于水的组份后留下了不溶的树脂组份基料。而且,虽然失效的涂膜可能含有高达30-40%毒物,但它不再控制污垢,因为将毒物渗至表面所需的水渗透受残留树脂基料的限制。这类失效的防污体系不能为重新涂布提供合适的衬底,因为在其涂膜中存在空隙,所以涂膜机械性能很差,因此它们对新涂层的粘合性较差。
将毒物加进水溶性聚合物并将它们用作防污涂料的试验也不能产生所需的结果。这种涂料在海水中会溶胀,因此可以料想它不能提供良好机械性能和均一控制污垢的能力,因为整个涂膜在长期的水浸泡中性能逐渐变差。
近年来,所谓的自磨光防污涂料越来越普遍。这些涂料是以甲基丙烯酸三丁基锡、甲基丙烯酸甲酯和丙烯酸2-乙基己酯之类的涂膜软单体的聚合物为基础。有机锡聚合物用作涂料粘合剂。所有这类涂料也含氧化亚铜或三有机锡化合物之类的毒物添加剂。另外也可包括颜料、触变剂之类的常规涂料添加剂。在一般的碱性海水中有机锡聚合物粘合剂逐渐水解,三丁基锡以活性防污剂的形式释放出来。水解形成的聚合物是水溶或水可溶胀的,这样易于从表面被流动的海水腐蚀掉,并露出新的涂层表面。不象沥滤涂料,这些涂料的主要优点是:毒物释放随时间是线性变化的,在涂料的使用期内所有毒物都被利用了。而且,在重新涂布前无需清除旧的自磨光涂料体系的残余物,因为残余物的组份基本上与原先涂布时相同,这一点与常规防污涂料不同,常规防污涂料在使用期后在船壳上留下性能差的、沥滤过的粘合剂基料。据称,该体系另外的优点是:因为涂膜的磨损而随时减少船壳表面的粗糙度。这种粗糙度的减少变成为船舶操纵者节省燃料。
航海船舶一般在船壳上有2-4层防污涂料,每层涂料有100微米厚,其涂膜总厚度为200-400微米。这种涂层的寿命预计约为5年。
为了商业上可接受,船用防污涂料应最好符合如下标准:
1.聚合物最好溶于易于涂布的涂料介质中;
2.聚合物最好具有良好的成膜性能;
3.涂膜最好具有与船表面良好的粘合性,并且是可挠曲的;
4.涂膜最好仅在涂层表面发生水解。这样可有控制地释放金属。
剩余的涂料表面易被流动的海水腐蚀。这种机理称为“自磨
光”并可观察到船舶燃料效率的显著提高;以及
5.聚合物最好具有有控制的释放特性。
因此,本发明针对新颖化合物以及含由这些化合物聚合而成的聚合物的船用防污涂料组合物。
本发明的其它特征和优点将在下面说明书中加以描述,一部分可从说明部分获知,一部分可从本发明的实施过程获知。本发明的目的和其它优点将借助于在说明书和所附权利要求书中特别指出的技术特征及其结合加以认识和实现。
发明的概述
为实现这些或那些在本文中记载并加以广义描述的,与本发明目的相一致的优点,本发明涉及通式(Ⅰ)表示的化合物:在该通式中,L1是主族原子。M是元素周期表中的过渡金属元素。换句话说,M是元素周期表第13、14、15或16族中的金属元素。x是M的氧化态。n是M的配位数,m表示与M相键合的(R1R2R3)L1配体的数目,m通常为1。
R1是可聚合基团。
R2和R3可以相同或不同,且为含高达15个碳原子的取代或未取代的烷基;含高达30个碳原子的取代或未取代的芳基;含高达15个碳原子的取代或未取代的烷氧基或烷硫基(thioalkyl);含高达20个碳原子的取代或未取代的芳氧基或芳硫基(thioaryl);含高达25个碳原子含氧或含硫杂环;取代或未取代的胺;取代或未取代的酰胺;或含高达25个碳原子的取代或未取代的氮杂环(当L1不为N时)。
R4是阴离子配体,且当x大于1时可以相同或不同。
最后,L2是中性配体。
在另一个方面,本发明将包括将一种或多种上述通式(Ⅰ)表示的,用在船用防污涂料中的化合物聚合成粘合剂,该粘合剂作为共杀生物剂也是有效的。
本发明也可涉及含由通式(Ⅰ)所示的单体聚合而成的聚合物的有控制的释放组合物。
另外,本发明涉及通过涂布含通式(Ⅱ)表示的化合物的组合物防止表面污垢的方法:式中,M、x、L2、n、和R4与通式(Ⅰ)中定义相同。
应该理解:前面一般描述和下面详细描述仅是示范性的和解释性的。详细的描述
本发明的一个方面涉及通式(Ⅰ)表示的新颖化合物:通式(Ⅰ)表示的化合物也可理解为单体,因为这些化合物通过与相同的单体或任何其它可加入聚合物中的单体结合能转化成聚合物。然后,可将由一种或多种通式(Ⅰ)表示的化合物与甲基丙烯酸甲酯之类的任何其它已知的单体聚合而成的聚合物作为粘合剂加入涂料配方中,以制成船用防污涂料组合物。
参阅通式(Ⅰ),L1是主族原子或优选的为元素周期表第15族中的元素。L1也可以是元素周期表第13、14或16族中的元素。本文所述的所有元素周期表中的族是按照Hawley’s Condensed ChemicalDictionary、第11版中所列的元素周期表的“新表示法”。因此,L1优选的为氮、磷、砷、锑或铋。L1最优选的为磷。
m表示与M键合的(R1R2R3)L1配体的数目。除下列例外以外,m通常为1。
当M为铜,x等于1,L1为磷,L2不存在(即n-(x+m)等于零),R4为氰酸根、硫氰酸根和异氰酸根时,m等于2;
当M为铜,x等于1,L1为磷,L2不存在(即n-(x+m)等于零),R4为含高达15个碳原子的取代或未取代烷硫基或含高达25个碳原子的取代或未取代芳硫基时,m等于3。
M是元素周期表中的过渡元素(即元素周期表中的3-12族)。
或者,M是元素周期表13-16族中金属元素。换句话说,M可以是Sc、Y、La、Ac、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Ge、Sn、Pb、Sb、Bi、Si、As、Te或Po。
M优选的为铜、锌或锡。M最优选为铜。
x表示M的氧化态。n是M的配位数。就目前所知,M所包括的现有元素的配位数n,视M而异,可以是2-9之间的一个整数。例如,
当M是包括Sc和Y的第3族元素时,
M的配位数为4或6(主要为6);以及
M的氧化态为+2、+3、+4(主要为+3)。
当M是第4族元素时,
M的配位数为4、5、6、7或8(主要为4或6);以及
M的氧化态为+4。
当M是第5族元素时,
M的配位数为4、5、6、7、8或9(主要为6);以及
M的氧化态为+3、+4或+5。
当M是第6族元素时,
M的配位数为3、4、5或6(主要为6);以及
M的氧化态为+2、+3、+4、+5或+6(主要为+2和+
3)。
当M是包括Mn、Re和Tc的第7族元素时,
M的配位数为4、5、6或7(主要为4或6);以及
M的氧化态为+2、+4、+5或+7。
当M是第8族元素时,
M的配位数为3、4、5、6、7或8(主要为6);以及
M的氧化态主要为+2、+3、+4、和+6。
当M是第9族元素时,
M的配位数为4、5或6;以及
M的氧化态主要为+1+2、+3、或+4。
当M是第10族元素时,
M的配位数为4或6;以及
M的氧化态主要为+2、和+4。
当M是第11族元素时,
M的配位数为2、4或6;以及
M的氧化态主要为+1和+2。
当M是第12族元素时,
M的配位数为2、4或6;以及
M的氧化态主要为+2。
当M是包括Al、Ga、In和Tl的第13族金属元素时,
M的配位数为3、4、5或6;以及
M的氧化态主要为+2或+3(主要为+3)。
当M是包括Si、Ge、Sn和Pb第14族金属元素时,
M的配位数为4、5或6;以及
M的氧化态主要为+2或+4。
当M是包括As、Sb和Bi的第15族金属元素时。
M的配位数为3、4、5、或6;以及
M的氧化态主要为+3或+5。
当M是包括Te或Po的第16族金属元素时,
M的配位数为4、5或6;以及
M的氧化态主要为+2、+4、或+6。
R1是可聚合基团。换句话说,R1是一种当将通式(I)所示化合物聚合成聚合物时的可聚合的取代基。对于本发明的目的,R1可以是任何类型的可聚合基团。它包括:
(1)任何带双键的单元,并可用如下通式表示:式中,R6为氢;含高达25个碳原子的烷基;含高达25个碳原子的烯基;R7为氢;含高达25个碳原子的取代或未取代的烷基;含高达25个碳原子的取代或未取代的芳基;卤素;含高达25个碳原子的取代或未取代的羧基;含高达25个碳原子的取代或未取代的酰胺基;氰酸酯基;异氰酸酯基;或硫氰酸酯基。在这种单元中,取代基R6或R7,较好的为R7与L1相键合。
(2)通过环内双键或开环聚合(ROMP)而聚合的环状单体。这些单体包括3-8元环,环内原子为取代或未取代的碳、羰基、氧、取代或未取代的磷、或取代或未取代的酰胺。碳原子的总数可高达40。
(3)带共活性(coreactive)官能团的单体,它包括如下几个:H2N-R8-NH2HO2C-R9-CO2HH2N-R10-CO2HHO-R11-OHCl-R12-ClClOC-R13-COCl 式中R8、R9、R10、R11、R12和R13各选自含高达25个碳原子的取代或未取代的烷基、含高达25个碳原子的取代或未取代的芳基、含高达25个碳原子的取代或未取代的硅烷、含高达25个碳原子的取代或未取代的氮杂环。另外,R8也可以是带共活性官能团的羰基,R基团(即R8-R13)与L1相键合。
R1优选的为丙烯酸酯基或甲基丙烯酸酯基。
R2和R3可以相同或不同,且为含高达15个碳原子的取代或未取代的烷基;含高达30个碳原子的取代或未取代的芳基;含高达15个碳原子的取代或未取代的烷氧基或烷硫基;含高达20个碳原子的取代或未取代的芳氧基或芳硫基;含高达25个碳原子含氧或含硫杂环;当L=N时,它们也可包括含高达25个碳原子的取代或未取代的胺,酰胺,或氮杂环(如吡啶)。
R14为含高达6个碳原子的烷基或表示一个R2和R3之间的键,R14优选的为一个R2和R3之间的键。
R4为阴离子配位体。阴离子配体的例子包括,但不限于,卤素、氰酸根、异氰酸根、硫氰酸根、最好不含能发生消除的α-或β-氢的烷基、含高达15个碳原子的取代或未取代的烷硫根、含高达25个碳原子的取代或未取代的芳硫根、含高达25个碳原子的含硫杂环、含高达25个碳原子的取代或未取代的芳氧根(aryloxide)、含高达15个碳原子的取代或未取代的烷氧根(alkoxide)、含高达25个碳原子的含氧杂环、含高达30个碳原子的取代或未取代的环戊二烯基和任一碳原子上氢原子至少有一个被卤素任意取代的乙酰丙酮根。当x为2或更高时,R4可以相同或不同。
R4优选的为卤素、氰酸根、异氰酸根或硫氰酸根。
当L2存在时,它是中性配体。例如,当[n-(x+m)]等于2或更大时,L2可以相同或不同。当L2与三个(对三价化合物而言)或二个(对二价化合物而言)相同或不同的取代基键合时(除与M连接的键以外),L2可以是三价磷化合物、三价砷化合物、三价锑化合物或二价硫化合物、二价硒化合物、二价碲化合物。例如,这些二价或三价化合物可带有卤素、含高达25个碳原子的取代或未取代的芳氧基或烷氧基、取代或未取代的烷基、取代或未取代的芳基之类的取代基。
或者,L2是取代或未取代的异氰酸烷基酯或异氰酸芳基酯;羰基或一氧化碳;硫代羰基或一硫化碳;亚硝酰基;取代或未取代的胺;取代或未取代的烷基或芳基腈;包括四氢呋喃(THF)的环状或直链醚之类的配位溶剂(coordinating solvent)。上述取代或未取代的不饱和烃基或芳基,这种烃基或芳基主要通过π键与M键合。
当n-(x+m)大于0(即1或更大)时,由于M有另外的配位位置,L2取代基将与M连接。当有一个以上的L2取代基时,每个L2取代基可以相同或不同或螯合(即相互连接)。例如,当M为铬(Ⅲ)时,n等于6,x等于3,m等于1,n-(x+m)等于2。将有二个L2取代基,例如,它们可以都为胺,或一个L2为胺,而另一个L2为膦。
通式(Ⅰ)的一个优选的通式为通式(Ⅱ):式中R15表示氢或含高达6个碳原子的直链烷基。
最优选的化合物有如下通式:在该通式中,M为在海水中有杀生物作用的Cu(Ⅰ)金属,X是Cl、SCN或SPh(苯硫基)。当X是Cl时,m=1;当X是SCN时,m=2;当X是SPh时,m=3。L1是形成亚磷酸酯部分的P。该亚磷酸酯部分将Cu的氧化态维持在+1,并水解成无机磷酸盐。将化合物的丙烯酸酯部分保持在自由基聚合位置。当被释放时,亚磷酸部分进一步增加了聚合物表面附近的酸性(即降低pH)。因为有较低的pH,所以在聚合物表面附近产生了对藤壶之类的海洋生物不适宜的环境。上述的化合物也可以与Cu2O进行电化学偶合,其中二个Cu(+1)离子转化为一个Cu(O)和一个Cu(+2),以更有效地释放Cu。
针对本发明的目的,下列定义可用于本申请中所用的术语。
未取代芳基定义为包括至少一个苯环的基团,苯环可以稠合或不稠合。“稠合”是指二个或多个芳族苯环共享至少一个碳原子,如联苯基或萘基。
取代芳基定义为在一个或多个芳环碳上连接下列物质的基团:至少含一个氮的配体,如叠氮化物、亚胺、酮亚胺、胺、酰胺或酰亚胺;至少含一个氧的配体,如醇、醚、酯、酮、醛、酸酐或羧酸之类的有机酸;至少含一个硫的配体,如硫醇、硫醚、二硫化物、砜、亚砜、磺酸酯或磺酸;取代或未取代的烷基。如本申请中所定义的烷基。
关于取代或未取代的芳基,也准备包括由Friedel Crafts型催化剂引发的甲基取代、乙基取代或其它包括卤代和酰卤代的烷基取代。换句话说,准备将任何芳基与某些取代基间的亲电或亲核型反应形成的产物包括到取代芳基部分。这种取代芳基的例子为:2,4,6-三甲基苯乙烯、α-甲基苯乙烯、间-溴代苯乙烯和间-甲基苯乙烯。
饱和或不饱和的、环状的、支链或直链的未取代烷基主要包括基本上仅由碳和氢组成的化合物。这种物质的例子包括满足通式CyH2y+1或CyH2y-1的化合物,式中y可以变化,如从1至20。对于环烷烃来说,y至少为3,对于带支链环烷烃来说,y至少为4。
饱和或不饱和的、环状的、支链或直链的取代烷基包括用至少一个氟、氯、溴或碘之类的卤素、至少一个氧、氮或硫取代本文所定义的未取代“烷基”中一个或多个氢产生的物质,其中氧任选地有至少一个与它相连接的另外的碳、氮或硫;氮任选地有至少一个与它相连接的另外的碳、氮或硫;硫任选地有至少一个与它相连接的另外的碳、氮或硫。取代烷基的例子包括如下化合物:胺、醇、酸、酯、酮、硫醚、砜、亚砜、异氰酸酯、氰酸酯、硫氰酸酯、腈和nitrosones。
关于上述通式(Ⅰ)化合物的制备方法,有各种方法可以使用。一般来说,通式(Ⅲ)表示的化合物与通式(Ⅳ)表示的化合物反应,通式(Ⅲ)中的L1、R1、R2和R3以及通式(Ⅳ)中的M、L2、R4、n、m和x具有与通式(Ⅰ)中相同的定义。Z1表示L1上的一对电子或一个官能团(即离去基团)。一般地说,Z1是可被中合适的键位(bond site)取代的任何官能团。Z1所包括的官能团的例子包括-OH、和卤素。当L1为氮、磷、砷、锑或铋时,Z1一般表示L1上一对可用电子对。当L1不是元素周期表中第15族元素而是如硫或硅之类时,Z1可以是-OH或卤素之类的官能团。
通式(Ⅲ)表示的化合物一般可购自Aldrich化学公司。
通式(Ⅲ)化合物(其中L1为磷)的具体例子和制备方法请参阅Pudovik等在Chemical Abstract,63卷1965年,13420页中关于亚磷酸酯的论述。该文献参考引用于本发明。
就通式(Ⅳ)化合物而言,Z2表示一个有合适取向的空轨道,它可接受电子对(Z1)形成L1-M键。另外,Z2可以是一个可与Z1反应形成独立的Z1Z2分子和L1-M键的官能团。这种官能团(即离去基团)的例子是氢负离子或卤离子。在这种情况下,Z2官能团与Z1离去基团连接形成一个化合物,通过L1开键和Mx开键形成通式(Ⅰ)化合物。
另外,当Z2表示乙腈之类的不稳定配体时,Z1或可表示一个电子对。在这种情况下,乙腈被自身所稳定,当从M上断开时,L1与Mx之间形成一个键。Z2也可表示M上一个空轨道位置,当Z1表示一个电子对时,该空轨道位置可从L1上接受电子。当M是Cu(Ⅰ)和L2是Cl时就是这种情况的一个例子。
通式(Ⅳ)化合物的例子包括,但不限于,CuCl、CuSCN、ZnCl2。这类化合物一般可购自Strem化学公司。和Aldrich化学公司。
根据上述观点,下面叙述了本发明中优选的通式(Ⅰ)化合物的更详细的制备方法。
下述化合物的制备一般按三步合成方法进行。第一步,由丙烯酸或甲基丙烯酸与氢氧化钠反应合成丙烯酸钠或甲基丙烯酸钠。例如,下列反应式表示甲基丙烯酸与氢氧化钠的反应。丙烯酸钠或甲基丙烯酸钠又与氯代亚磷酸二乙酯反应,产生亚磷酸丙烯酰二乙酯(acrylodiethylphosphite)或亚磷酸(甲基丙烯酰)二乙酯(methacrylodiethyl-phosphite)。例如,如下的反应式表示制备亚磷酸(甲基丙烯酰)二乙酯的反应。亚磷酸丙烯酰二乙酯或亚磷酸(甲基丙烯酰)二乙酯又且较好地在原处与CuX(X=Cl、SCN、SPh(苯硫基))反应,形成亚磷酸丙烯酰二乙酯合铜或亚磷酸(甲基丙烯酰)二乙酯合铜。例如,下列反应式表示CuX与亚磷酸(甲基丙烯酰)二乙酯的反应。这些含磷化合物都缩写为“P”后面接金属的化学符号(这里为铜)和词“单体”。因此亚磷酸丙烯酰二乙酯合铜缩写为“PCuX单体”,相应的锌金属单体缩写为“PZuX单体”。前面叙述了一个CuCl的合成方法,但同样的反应也可用于制备CuSCN和CuSPh以及M所包括的其它金属化合物。
未反应的丙烯酸或甲基丙烯酸、水或CuX的存在会导致不需要的副反应。因此,应彻底洗去丙烯酸钠或甲基丙烯酸钠,以清除任何未反应的丙烯酸或甲基丙烯酸。然后应将残余的沉淀物干燥(例如,用真空泵或水-二甲苯共沸蒸馏的方法,所用的温度最好地保持在约35℃以下,且同时抽真空)。水的存在会引起亚磷酸丙烯酰二乙酯或亚磷酸甲基丙烯酰二乙酯的不需要的水解,产生磷酸酯,释放出丙烯酸。
在所述的亚磷酸酯合铜存在下丙烯酸酯基或甲基丙烯酸酯基倾向于自聚。因此,建议使用冷浴和用较多的溶剂稀释。溶液温度最好低于约15℃,但在低于约5℃时,可能观察到亚磷酸酯的不完全结合(incorporation),应加以避免。
PCuX单体系列(series)受稳定的CuX化合物数目所限制。PCuX单体一般是无色或淡黄色的粘性液体,它应在热或光的影响下聚合。
每个CuX单元中亚磷酸酯的数目会视X的不同而变化的。例如,在CuCl的情况下,每个CuCl中仅有一个亚磷酸酯。在CuSCN的情况下,每个CuSCN中有二个亚磷酸酯。在CuSPh的情况下,每个CuSPh单元中有三个亚磷酸酯。
PCuCl单体的紫外光解产生青色(green white)固体和二种磷酸酯。换句话说,Cu被释放了。氯代磷酸二乙酯的存在表明:Cu-L1键(如Cu-P)发生了均裂,然后重排释放出磷酸酯。(参阅Rxn(a))。对于PCuSCN单体和PCuSPh单体,观察到了相同的分解反应。(参见Rxn(b)和(c))。PCuX单体的电化学性能用循环伏安法加以测量。电化学电池在1×103M饱和六氟磷酸四丁基铵的二氯甲烷溶液中含有10毫升PCuX单体。参比电极是饱和甘汞电极(SCE),工作电极是碳,辅助电极是铂。遵守的操作步骤见CV-27 Cyclic Voltammographmanual。单体的电化学研究得到如下的结果:
还原电势 氧化电势[H2C=C(CH3)C(O)O](EtO)2PCuCl -1.00 eV 1.375 eV{[H2C=C(CH3)c(O)O)](ErO)2P}3CuSPh -1.350 eV 0.935 eV[H2C=C(CH3)C(O)O](EtO)2PCuSBut -1.355 eV 0.875 eV电化学结果是适当的,因为它们表示铜化合物可与另一种铜(+1)化合物(Cu2O)偶合,产生Cu(O)和Cu(+2)配合物(反应(d))。这可有助于有控制地释放两种铜物质。 (d)如上所述,通式(Ⅰ)的化合物一旦形成,这种化合物可与一种或多种其它单体聚合成一种聚合物。通式(Ⅰ)的化合物最好与甲基丙烯酸酯单体和丙烯酸酯单体之类的涂膜软单体聚合形成三元共聚物。除M是Cu(Ⅱ)的情况以外,最好地将通式(Ⅰ)的化合物与一种或多种涂膜软单体和甲基丙烯酸酯之类的单体按自由基机理进行聚合。另外,也可将通式(Ⅰ)的化合物与一种或多种涂膜软单体和甲基丙烯酸酯之类的单体进行缩聚。应该使用溶剂,以便聚合物在溶剂中仍保持可溶。一般来说,酮溶剂是优选的,甲乙酮是最优选的。聚合反应最好地用自由基引发剂进行引发。一旦聚合,聚合物可能有如下重复单元:然而,单体是无规连接到聚合物上的。
涂膜软单体的例子包括,但不限于,取代或未取代的丙烯酸酯单体,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、丙烯酸异辛酯、甲基丙烯酸2-乙基己酯、丙烯酸壬酯、甲基丙烯酸壬酯、甲基丙烯酸月桂酯、甲基丙烯酸十八烷酯、丙烯酸(二甲氨基乙)酯、甲基丙烯酸(二甲氨基乙)酯、甲基丙烯酸三氟乙酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸叔丁氨基乙酯。
尤其是,现已发现,当使用某些自由基引发剂时,可以将上述物质的丙烯酸酯组份的不饱和键聚合。然而,用过氧化氢或如羧基过氧化苯甲酰之类的有机过氧化物的引发剂使这种单体聚合通常会使铜(Ⅰ)氧化至铜(Ⅱ)并破坏含铜单体。
特别适用于本发明含铜单体的自由基引发剂优选地包括偶氮化合物,如偶氮腈、偶氮脒、烷基取代的偶氮化合物、在一个α碳上被取代并与如下一种或多种化合物相结合的偶氮化合物:醇、酯、腈、酰胺、氨基醇、及其取代的胺和酰胺。
由Wako Pure Chemical Industries Ltd.出售的偶氮腈的例子是:偶氮腈化合物:2,2′-偶氮二(4-甲氧基-2,4-二甲基戊腈)、2,2′-偶氮二(2,4-二甲基戊腈)、2,2′-偶氮二(2-甲基丙腈)、2,2′-偶氮二异丁腈、2,2′-偶氮二(2-甲基丁腈)、1,1′-偶氮(环己烷-1-腈)、1-〔(1-氮基-1-甲乙基)偶氮〕甲酰胺、2-(氨基甲酰偶氮)异丁腈、2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈;偶氮脒化合物:2,2′-偶氮二(2-甲基-N-苯基丙脒)·二氯化氢、2,2′-偶氮二〔2-(N-苯脒基)丙烷〕·二氯化氢、2,2′-偶氮二〔N-(4-氯苯基)-2-甲基丙脒〕·二氯化氢、2,2′-偶氮二〔N-(4-氯苯基)脒基〕丙烷·二氯化氢、2,2′-偶氮二〔N-(4-羟苯基)-2-甲基丙脒〕·二氯化氢、2,2′-偶氮二2-〔N-(4-羟苯基)脒基〕丙烷·二氯化氢、2,2′-偶氮二〔2-甲基-N-(苯甲基)-丙脒〕·二氯化氢、2,2′-偶氮二〔2-甲基-N-(2-丙烯基)丙脒〕·二氯化氢、2,2′-偶氮二〔2-(N-烯丙基脒基)丙烷〕·二氯化氢、2,2′-偶氮二(2-甲基丙脒)·二氯化氢、2,2′-偶氮二(2-脒基丙烷)·二氯化氢、2,2′-偶氮二〔N-(2-羟乙基)-2-甲基丙脒〕·二氯化氢、2,2′-偶氮二〔2-(N-2-羟乙基)脒基〕丙烷·二氯化氢;偶氮酰胺:2,2′-偶氮二2-甲基-N-〔1,1-二(羟甲基)-1-羟乙基〕丙酰胺、2,2′偶氮二2-甲基-N-〔1,1-二(羟甲基)乙基〕丙酰胺、2,2′-偶氮二〔2-甲基-N-(2-羟乙基〕丙酰胺〕、2,2′偶氮二(2-甲基丙酰胺)·二水、2,2′-偶氮二(异丁酰胺)·二水;烷基偶氮化合物:2,2′-偶氮二(2,4,4-三甲基戊烷)(偶氮二叔辛烷)、2,2′-偶氮二(2-甲基丙烷)(偶氮二叔丁烷)和在α碳上被取代并与如下一种或多种化合物相结合的偶氮化合物:醇、酯、腈、酰胺、氨基醇、及其取代的胺和酰胺。其它的例子包括:2,2′-偶氮二(2-甲基丙酸二甲酯)、2,2′-偶氮二异丁酸二甲酯、4,4′-偶氮二(4-氰基戊酸)、4,4′-偶氮二(4-氰基戊酸)、2,2′-偶氮二〔2-(羟甲基)丙腈〕。
虽然有机过氧化物引发剂一般不适用于聚合或共聚本发明的含铜单体,但当用其它金属代替铜时,这种引发剂适用于聚合本发明范围内含其它金属的单体。这种替代引发剂的例子是:过氧化有机磺酰、过氧化二烷基、过氧化二芳基、过氧化烷基芳基、过氧化二酰基、过氧化酮、过氧缩酮、过二碳酸酯、过碳酸酯和过氧化酯。
这类物质的实例可购自Elf Atochem North America,Inc.,商品名为LUCIDOL。这类化学物质的具体例子是:过氧化二酰基,如过氧化2,4-二氯苯甲酰、过氧化二异壬酰、过氧化癸酰、过氧化月桂酰、过氧化丁二酸、过氧化乙酰、过氧化苯甲酰(benzoyl peroxide);过氧化酮,如过氧化2,4-戊二酮;过二碳酸酯,如过二碳酸二正丙酯、过二碳酸二仲丁酯、过二碳酸二(2-乙基己)酯、过二碳酸二(2-苯氧基乙)酯;过氧化酯,如过新癸酸α-枯基酯、过新戊酸α-枯基酯、过新癸酸叔丁酯、过新戊酸叔丁酯、2,5-二甲基-2,5-二(过-2-乙基己酰氧基)己烷、过-2-乙基己酸叔丁酯、过异丁酸叔丁酯、过马来酸叔丁酯、2,5-二甲基-2,5-二(过苯甲酰氧基)己烷、过乙酸叔丁酯、过苯甲酸叔丁酯、二过邻苯二甲酸二叔丁酯、过新戊酸叔戊酯;过氧化二烷基,如过氧化二枯基、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、过氧化二叔丁基、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3;氢过氧化物,如2,5-二氢过氧基-2,5-二甲基己烷、叔丁基过氧化氢;过缩酮,如1,1-二(叔丁基过氧基)-3,3,5-三甲基环己烷、1,1-二(叔丁基过氧基)环己烷、2,2-二(叔丁基过氧基)丁烷、3,3-二(叔丁基过氧基)丁酸乙酯。
另外,一种或多种如下的取代或未取代的单体可与通式(Ⅰ)的单体聚合:丙烯酸酯、丙烯醛、丙烯腈、丙烯酰胺、丙烯酰卤、烯丙基类(allyls)、丁二烯、柠康酰亚胺、二烯丙基类(diallyls)、异戊二烯、衣康酸、衣康酰胺酸酯、衣康酰亚胺、马来酸烷基酯、马来酸酐、马来酰亚胺、甲基丙烯酰胺、甲基丙烯酸烷基酯、甲基丙烯酸或甲基丙烯酸酐、噁唑啉、吡咯烷酮、苯乙烯、乙烯基类(vinyls)和亚乙烯基二卤。它们的一些典型例子为:关于丙烯酸酯:丙烯酸(α-乙酰氧基乙)酯、丙烯酸α-氯代甲酯、丙烯酸(α-三氟甲基甲)酯、丙烯酸苄酯、丙烯酸乙酯、丙烯酸(二茂铁基甲)酯、丙烯酸异丁酯和丙烯酸苯酯;关于丁二烯:2,3-二氯丁二烯、2-氯丁二烯;丙烯酰胺、α-氟代丙烯酰胺、N-十八烷基丙烯酰胺;丙烯酸酯、α-氯代丙烯酸甲酯、α-氟甲基丙烯酸甲酯、丙烯酸苄酯、丙烯酸乙酯、丙烯酸(二茂铁基甲)酯、丙烯酸异丁酯、丙烯酸苯酯;丙烯酸、α-溴代丙烯酸;丙烯腈、α-三氟甲基丙烯腈;烯丙基类、烯丙醇;丁二烯、2,3-二氯丁二烯、2-氯丁二烯;柠康酰亚胺、N-苄基柠康酰亚胺、N-丁基柠康酰亚胺N-异丁基柠康酰亚胺;二烯丙基类,密胺二烯丙基(melamine diallyl)、邻苯二甲酸二烯丙基酯、二烯丙基氨腈;异戊二烯、3-乙酰氧基异戊二烯、乙酸异戊二烯基酯;N-苯基衣康酰胺酸乙酯;衣康酸二丁酯、衣康酸、衣康酰亚胺;N-苄基马来酰亚胺、N-4-羟苯基)马来酰亚胺、N-苄基马来酰亚胺、N-丁基马来酰亚胺、N-苯基马来酰亚胺;甲基丙烯酰胺、N-(甲氧基甲基)甲基丙烯酰胺、N-苯基甲基丙烯酰胺;甲基丙烯酸烷酯、甲基丙烯酸苄酯、甲基丙烯酸氯甲酯、甲基丙烯酸(氰基甲)酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸(2-羟基乙)酯、甲基丙烯酸(2-羟基丙)酯、甲基丙烯酸(2-苯乙)酯;甲基丙烯酸;甲基丙烯酸酐;噁唑烷酮、N-乙烯基噁唑烷酮、吡咯烷酮、α-亚甲基-N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、1-苄基-3-亚甲基-5-甲基吡咯烷酮;苯乙烯、α-甲基苯乙烯、2,4,6-三甲基苯乙烯、2,5-二氯苯乙烯、间溴苯乙烯、间氯苯乙烯、间甲基苯乙烯、对溴苯乙烯、对氯甲基苯乙烯、对-N,N-二甲氨基苯乙烯;乙烯基类、乙酸乙烯酯、苯甲酸乙烯酯、溴乙烯、丁酸乙烯酯、氯乙烯、乙烯基醚、乙基乙烯基醚、乙基·乙烯基酮、草酸乙·乙烯酯、乙基乙烯基硫醚、乙基乙烯基亚砜、苯基乙烯基酮、丙酸乙烯酯、乙烯砜、乙烯基二茂铁、乙烯基氢醌、乙烯基氢醌二苯甲酸酯、亚乙烯基类、亚乙烯基二氯、亚乙烯基二氰、异氰酸乙烯酯、乙烯基三甲基硅烷。
单体的选择取决于每种有控制的释放用途所需的性质。例如,用作船用防污剂的聚合物必须形成有良好机械完整性的可挠曲涂膜。因此,通式(Ⅰ)的单体必须与可得到挠性的橡胶状单体(如丙烯酸丁酯)和可获得良好的机械性能的硬单体(如甲基丙烯酸甲酯)聚合。
本发明的PCuCl和其它过渡金属单体在MEK中与丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)聚合产生Mw在约50,000-60,000之间的聚合物溶液。
该聚合物以悬浮状保存在酮、更好的为甲乙酮之类的溶剂中,它可用粘合剂。然后按本技术领域中熟练技术人员已知的方法加入颜料、染料和其它杀生物剂。这些组份及其加入这些组份制成涂料的方法的描述请参阅下列一本参考引用的技术书:MarineBiodeterioration:An Inerdisciplinary Study,J.D.Costlaw andR.C.Tipper,Eds.,Naval Institute Press,Annapolis,Maryland,1984,特别注意如下一章:"The Chemical and PhysicalCharacterization of Marine Coatings Containing OrganotinAntifoulants″by M.L.Good and C.P.Monaghan。
一旦制成涂料,这种涂料就可涂在船壳之类的表面,涂布时溶剂(如酮)挥发,留下聚合物和其它组份。所用溶剂最好有长烷基链,这样可使溶剂慢慢挥发,有助于避免在涂料内层滞留溶剂。
按本发明制得的优选的有机金属聚合物可达到如下几点:
1.为便于涂布,聚合物是可溶于溶剂。
2.聚合物溶液能形成有足够挠性的透明硬膜,以便涂布船的表面。
3.涂膜至少发生部分表面水解,以释放金属,变成溶解或溶胀的材料而被磨损或溶解掉,同时产生新的聚合物层,这种聚合物层最好是光滑的,以保持船的燃料效率。
本发明的聚合物也可以有控制地释放活性剂。有控制的释放体系可使活性化学剂以规定的速度和时间转化为规定的产物,以达到所需的效果。这种活性化学剂包括:Cu2O、亚乙基双(二硫代氨基甲酸根)合镁(Maneb)、二甲基二硫代氨基甲酸根合锌(Ziram)、2-环丙氨基-4-异丁氨基-6-甲硫基-S-三嗪、N′-(3,4-二氯苯基)-N,N-二甲基脲(Diuron)、亚乙基双(二硫代氨基甲酸根)合锌(Zineb)、N-(氟二氯甲硫基)邻苯二甲酰亚胺(Fluorofolpet)、N,N-二甲基-N′-苯基-N′-(氟二氯甲基)硫代硫酰胺(Dichlorofluanide,Euparen)、二硫化四甲基秋兰姆(Thiram)、亚甲基二硫脲、4-丁基邻苯二酚、Captan、二甲基二硫代氨基甲酸根合锌、2-甲硫基-4-叔丁氨基-6-环丙氨基-S-三嗪、2,4,5,6-四氯间苯二氰、N,N-二甲基-N′,N′-二氯苯基脲、硫氰酸铜、4,5-二氯-2-正辛基-3(2H)异噻唑酮、N-氟二氯甲硫基邻苯二甲酰亚胺、N,N-二甲基-N′-苯基-N′-(氟二氯甲硫基)硫酰胺、2-巯基-1-氧化吡啶锌盐、二硫化四甲基秋兰姆、铜-镍(10%)固体溶液合金、2,4,6-三氯苯基马来酰亚胺、2,3,5,6-四氯-4-甲磺酰吡啶、氨基甲酸(3-碘-2-丙烯基丁)酯、二碘甲基对甲苯甲酰砜、双(二甲基二硫代氨基甲酸锌)亚乙基双(二硫代氨基甲酸酯)(Bis-(demethyldithiocarbamoyl zinc)ethylene bis-dithiocarbamate)、吡啶·三苯基硼、2-巯基-N-氧化比啶锌(Zinc Omadine)(1-羟基-2-吡啶硫酮的锌盐)、四氯间苯二氰(NuoCide 960s)(Chlorothalonil)、1-甲硫基-3-叔丁氨基-5-环丙氨基-S-三嗪(Irgarol 1051)、4,5-二氯-2-正辛基-3(2H)异噻唑酮(isothiazolone)/氯-2-正辛基-3(2H)异噻唑酮7/1(防污剂3-9211M)、异噻唑酮、有机硫杀生物剂(Rohm&Haas,费城)。这些体系在许多领域内得到了越来越多的应用。例如,医药、催化剂、杀虫剂和防污剂中。对于本发明的目的,有控制的释放体系的基本组份包括活性剂和控制活性剂释放的聚合物基料。聚合物体系的用途取决于它的性质,而这些性质可为每一种有控制的释放用途定制的。含本发明化合物的特别有用的有控制的释放体系是“可腐蚀体系”。具体地说,将活性剂掺合溶解,物理分散或化学结合到聚合物基料中。聚合物在使用过程中可溶或可降解,由于腐蚀作用,活性剂通过扩散或析出而被释放出来。本发明所述的含金属聚合物体系是指通过水之类的环境物质的表面腐蚀作用会释放活性剂的释放体系。
有控制的释放体系的主要优点是:这种体系允许使用少得多的活性剂,而在给定的时间内产生更好的效果。例如,杀虫剂或杀生物剂可有控制地在很长的时期内释放。一个具体的例子是本发明的船用防污剂有控制的释放体系,这种释放体系将船用涂料的寿命从二年延长至五年。
另外,本发明涉及到通式(Ⅱ)表示的金属配合物:式中M、x、L2、n、R4的定义与通式(Ⅰ)相同。通式(Ⅱ)的化合物可作为添加剂用到这种涂料组合物中,以防止易于结污垢的表面上的结垢。将金属配合物掺入涂料配合物之类的组合物中的方法以及将组合物涂布到表面(如船壳)上的方法对于本行业中熟练技术人员来说是已知的。
在下列实施例中,比较了如上所述的在聚合物中加入铜和不加入铜的效果差别。
为获得最佳成膜性质,用本发明单体和方法制成的聚合物的平均分子量较好的为约5000-200,000,更好的为约10,000-75,000。平均分子量按美国标准试验方法(ASTM)D 5296-92进行测量。
根据上面描述和下面具体实施例,本技术领域中的熟练技术人员一般可按下述的步骤制备通式(Ⅰ)的所有化合物。
实施例单体的合成实施例1:[H2C=C(CH3)C(O)O]P(OEt)2的合成
将稍过量的甲基丙烯酸在二甲苯中与氢氧化钠反应,生成甲基丙烯酸钠和水。收集甲基丙烯酸钠固体并用二甲苯和庚烷洗涤,直到检测不到甲基丙烯酸为止,然后真空下除去残余的痕量水。表1中列出了合成有关的准确数据。
表1:甲基丙烯酸钠的合成物质 分子量 摩尔数 加入量(克)甲基丙烯酸 86.09 1.18 100氢氧化钠 40.00 1.125 45二甲苯 106.17 650二甲苯洗涤 400庚烷洗涤 350总加入量: 15451.将650克二甲苯加入3升四颈烧瓶中。2.将二甲苯脱气。3.将100克甲基丙烯酸加入到反应瓶中。4.在3小时内分三等份加入45克氢氧化钠。5.在氮气氛中搅拌2天。6.在Schlenk过滤器中收集甲基丙烯酸钠。7.将甲基丙烯酸钠用二甲苯洗三遍(总量:400克)和用庚烷洗三遍(总量:350克)。8.抽去残余的溶剂和水,在真空下干燥2天。
然后将甲基丙烯酸钠和氯代亚磷酸二乙酯在庚烷中稀溶液反应几小时,生成亚磷酸(甲基丙烯酰)二乙酯和氯化钠。控制反应,以确保将所有的氯代亚磷酸乙酯反应掉。使用稍过量的(1.15)甲基丙烯酸钠。将氯化钠过滤掉,得到亚磷酸甲基丙烯酰二乙酯的庚烷溶液。将这种亚磷酸酯按以下实施例2中所述的方法与氯化亚铜在原处(in situ)反应。表2 列出了这种合成所需的准确数据。
该亚磷酸酯的表征结果:GC-MS(母离子=206.10),IR光谱〔ν(CO)=1708 cm-1和υ(P-O)=1027 cm-1,以及31P-NMR光谱(134ppm)。实施例2:[H2C=C(CH3)C(O)O]P(OEt)2CuCl的合成
将氯化亚铜加入到上述已冷却到2-5℃的亚磷酸(甲基丙烯酰)二乙酯的庚烷溶液中。有一个粘性紫色层离析出来,并将其以紫色油分离。将该粘性紫色油搅拌,它变成棕色油。将这样制成的[H2C=C(CH3)C(O)O]P(OEt)2CuCl配合物用庚烷洗涤。将未反应的氯化亚铜从上述配合物的甲乙酮溶液中过滤掉。表2也列出了这种合成的准确数据。
表2:氯化亚铜单体的合成物质 分子量 摩尔数 加入量(克)甲基丙烯酸钠 108.08 139 15ClP(OEt)2 156.55 124 19CuCl 98.99 91 9庚烷 200庚烷洗涤 50甲乙酮 16总加入量 3091.在烘箱中干燥玻璃仪器。安装玻璃仪器并用热风器进一步干燥。2.在氮气氛下将甲基丙烯酸钠加入反应瓶中。3.用套管将200克干燥的庚烷加入到反应瓶中。4.将反应溶液保持在2-5℃(冷水浴)。5.搅拌溶液并注射滴加ClP(OEt)2。将溶液温度保持在10℃以下。6.继续搅拌2小时。注意:当在GC-MS光谱上检测不到ClP(OEt)2时,反应已进行完全了。7.将氯化钠副产物过滤掉,并将反应溶液冷却到10℃。8.在1小时内将氯化亚铜加入反应溶液中。在氯化亚铜加入过程中将溶液温度保持在10-13℃之间。注意:产物为紫色油,继续搅拌时它变成棕色。9.用注射器抽去庚烷层。10.加入16克MEK并加以过滤。注意:用1H-和31P-NMR光谱表征氯化亚铜单体。
11.将MEK氯化亚铜单体的溶液用于聚合。如果氯化亚铜单体不立刻使用,需将溶液储存于冰箱中。CuSPh和CuSBu-t合成步骤类似于文献1中所述的步骤。
元素分析表明:P∶Cu∶Cl摩尔比为1∶1∶1。NMR光谱表明:亚磷酸酯是完整的,且与Cu相键合。由于磷与63Cu(丰度=69.1%)和65Cu(丰度=30.9%)的偶合,峰移向高场,即从134移到120ppm,峰也变宽了。63Cu和65Cu的自旋都为3/2。IR光谱产生的ν(CO)峰在1720 cm-1处,它原在1708 cm-1处。实施例3:{[H2C=C(CH3)C(O)O](OEt)2P}2CuSCN的合成
将CuSCN悬浮在庚烷中,并与[H2C=C(CH3)C(O)O](OEt)2P的庚烷溶液混合。在原处制备稍过量的亚磷酸酯(约10%),并在室温和搅拌下至少反应12小时。将所得的{[H2C=C(CH3)C(O)O](OEt)2P}2CuSCN分离为过滤过的黄色油。
IR光谱在1723 cm-1处产生ν(CO)峰,在1024 cm-1处产生亚磷酸酯峰,在2115 cm-1处产生ν(SCN)峰。实施例4:{[H2C=C(CH3)C(O)O](OEt)2P}3CuSPh的合成
CuSPh是在无水乙醇中由Cu2O和HSPh的1∶2摩尔比混合物制成。将该混合物加热回流,直至产生嫩黄色的CuSPh沉淀为止,基本上所有的Cu2O都已反应成苯硫酚铜。用乙醇和二甲苯洗涤沉淀。
然后将CuSPh化合物在庚烷溶剂中与[H2C=C(CH3)C(O)O]P(OEt)2进行反应。生成黄色溶液,该溶液易于慢慢光分解。由于ν(CO)IR光谱在1791、1733和1717 cm-1处产生多重峰。实施例5:CuCl-MMA-BA三聚物的合成
表3列出了CuCl单体与甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)聚合的细节。在起始溶液中固体的组成为:27%(摩尔)CuCl单体、65%(摩尔)MMA和8%(摩尔)丙烯酸丁酯(BA)。溶液的最后组成为80%(重量)MEK。加入BA是为了使聚合物更易挠曲,以此补偿MMA组份的刚性。
表3:CuCl单体与MMA和BA聚合分子量 加入量物质 (克/摩尔) 摩尔数 (克)CuCl单体 305.2 0.085 26甲基丙烯酸甲酯 100.12 0.205 20.5(MMA)丙烯酸丁酯(BA) 128.17 0.025 3.2AIBN 164.21 0.006 1甲乙酮(MEK) 72.11 0.006 199总加入量 249.71.在500毫升四颈烧瓶中加入20.5MMA、3.2BA和175克MEK。2.将溶液脱气30分钟。3.将烧瓶放入一个空气加热套(a heated mantled air-jack)中。4.将烧瓶加热至80℃。注意:为尽量减少不溶固体物的形成,必须猛
烈搅拌。5.经注射泵在4小时内加入10毫升AIBN的MEK溶液。同时经注
射泵在3小时内加入20毫升MEK和CuCl单体的溶液。6.在80℃再加热10小时。7.保留聚合物溶液的可溶部分。注意:表征LOD(溶解损失),并
用1H-和31P-NMR光谱进行表征。
实施例6:腐蚀研究
成膜性质曾用PCuCl单体与甲基丙烯酸甲酯和丙烯酸丁酯的三聚体进行了说明。使用实施例5所述方法制成的聚合物溶液、将聚合物的MEK溶液放在砂磨玻璃纤维盘中,并让MEK溶液在环境温度下蒸发三天。生成一个硬膜。
在人造海水中测试聚合物粘合剂的腐蚀能力。聚合物溶液用如下重量比的氧化亚铜和Bentone 27制成。
成份 Pts/wt
聚合物固体 10.00
氧化亚铜 20.00
Bentone 27 1.0
将上述混合物倒入一个白铁罐,并用涂料震荡器进行混合。氧化亚铜是辅助毒物,一般将它加入大多数防污剂配方物中。当聚合物溶液的固体含量低时,必须加入增稠剂(Bentone 27),以防止氧化亚铜从溶液中沉淀出来。将这种加过颜料的溶液放在砂磨玻璃纤维盘中,让其干燥三天。将该盘放在循环人造海水容器中,定时加以检测。观察到如下结果。
1.浸入一天后,观察到小绿点,并随后消失。以后得到均一的涂膜,并观察到表面腐蚀。
2.浸入试验二周后,将该盘在一个流动人造海水烧杯中放置三天。水溶液中铜释放率(%Cu)的测试表明:它与有机锡抑制相差无几(1.84 ppm对1.11ppm)。
3.该涂膜完整性和与盘的粘合性均良好。
几种影响这种氯化亚铜单体聚合的不同因素确定如下:
1.一般要求的引发剂是AIBN(2,2′-偶氮二异丁腈)类化合物。过氧化苯甲酰会将Cu(Ⅰ)氧化到Cu(Ⅱ),即溶液会从无色变为深紫色。观察到聚合所需的AIBN最小量一般约为0.5%(摩尔),以所有单体的总摩尔数为基准。
2.反应温度最好约为80℃。
3.AIBN和CuCl的加入速率都是重要的,且最好以相同的速率同时分别加入到含酮或甲乙酮之类的酮溶剂和共聚单体(MMA和/或BA)的反应介质中。加入速率视共聚单体而定,一般需要超过几小时。所用的AIBN量在0.5至2.0%(摩尔)之间,以所有单体的总摩尔数为基准。有时会形成不溶的固体。不溶固体部分的NMR光谱表明已形成了聚合物。
本文讨论的具体组合物、方法或实施方案对所要求保护的本发明来说仅是解释性的。根据本文的叙述,它们的任何变化对本行业中熟练技术人员来说都是显而易见的,因此这些变化都将包括在本发明的范围中。例如,在实施例中只明确地讨论了仅含铜的聚合物。其它的聚合物基本上用相同的方法通过在所述的合成过程中用不同的金属取代部分或全部的铜而制成。
例如,如Cu2O或CuSCN在树脂基质中是相容的或可以制成,它们可作为有用的添加剂加入树脂组合物中,这样一类已知防污剂也应包括在本发明范围中。
另一个例子是,将含铜(Ⅰ)的丙烯酸酯-亚磷酸酯配位物质水解和氧化成磷酸酯,然后转化成磷酸官能团的事实用作视磷酸酯中有机部分的长度不同控制pH和水解速率的方法。另外,控制聚合物形成之后和加入最后涂料之前的水解量为控制不同形式的防污金属的有效性或改变聚合物极性和/或水解性提供了有用途径。
在研究了本文所公开的本发明的说明和实施方法后,本发明的其它实施方案对本技术领域中熟练技术人员来说是显而易见的。应该认为,上述说明和实施例仅是示范性的,本发明的确切范围和精神由如下权利要求书加以说明。
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- 1995-12-20 TW TW084113660A patent/TW332820B/zh active
-
1996
- 1996-01-09 PT PT96100214T patent/PT723967E/pt unknown
- 1996-01-09 DK DK96100214T patent/DK0723967T3/da active
- 1996-01-09 DE DE69612410T patent/DE69612410T2/de not_active Expired - Fee Related
- 1996-01-09 ES ES96100214T patent/ES2156222T3/es not_active Expired - Lifetime
- 1996-01-09 EP EP96100214A patent/EP0723967B1/en not_active Expired - Lifetime
- 1996-01-24 CA CA002167960A patent/CA2167960C/en not_active Expired - Fee Related
- 1996-01-26 CN CN96102548A patent/CN1063752C/zh not_active Expired - Fee Related
- 1996-01-29 JP JP8033090A patent/JPH08253493A/ja not_active Abandoned
- 1996-01-29 BR BR9600251A patent/BR9600251A/pt active Search and Examination
- 1996-01-29 RU RU96101805/04A patent/RU2198890C2/ru not_active IP Right Cessation
- 1996-01-29 NO NO19960369A patent/NO314942B1/no not_active IP Right Cessation
- 1996-01-29 KR KR1019960001857A patent/KR100419111B1/ko not_active IP Right Cessation
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1997
- 1997-03-25 US US08/823,707 patent/US5786392A/en not_active Expired - Fee Related
-
2000
- 2000-08-01 CN CNB001225391A patent/CN1172940C/zh not_active Expired - Fee Related
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2001
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Also Published As
Publication number | Publication date |
---|---|
KR960029342A (ko) | 1996-08-17 |
ES2156222T3 (es) | 2001-06-16 |
RU2198890C2 (ru) | 2003-02-20 |
CA2167960A1 (en) | 1996-07-31 |
CN1172940C (zh) | 2004-10-27 |
EP0723967B1 (en) | 2001-04-11 |
NO314942B1 (no) | 2003-06-16 |
CA2167960C (en) | 2001-06-19 |
EP0723967A1 (en) | 1996-07-31 |
DE69612410T2 (de) | 2001-10-04 |
PT723967E (pt) | 2001-10-30 |
US5786392A (en) | 1998-07-28 |
TW332820B (en) | 1998-06-01 |
GR3035904T3 (en) | 2001-08-31 |
NO960369L (no) | 1996-07-31 |
BR9600251A (pt) | 1997-12-23 |
CN1295075A (zh) | 2001-05-16 |
KR100419111B1 (ko) | 2004-07-01 |
JPH08253493A (ja) | 1996-10-01 |
US5637745A (en) | 1997-06-10 |
DK0723967T3 (da) | 2001-06-18 |
CN1140176A (zh) | 1997-01-15 |
NO960369D0 (no) | 1996-01-29 |
DE69612410D1 (de) | 2001-05-17 |
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