CN100467511C - 作为封端剂用的环酮 - Google Patents
作为封端剂用的环酮 Download PDFInfo
- Publication number
- CN100467511C CN100467511C CNB028135504A CN02813550A CN100467511C CN 100467511 C CN100467511 C CN 100467511C CN B028135504 A CNB028135504 A CN B028135504A CN 02813550 A CN02813550 A CN 02813550A CN 100467511 C CN100467511 C CN 100467511C
- Authority
- CN
- China
- Prior art keywords
- ester
- acid
- polyisocyanates
- organic multiple
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 150000003997 cyclic ketones Chemical class 0.000 title claims description 20
- 239000002981 blocking agent Substances 0.000 title 1
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 68
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 23
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- -1 cyclopentanone-2-carboxylic acid nitriles Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 150000001408 amides Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 150000007945 N-acyl ureas Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 125000005594 diketone group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- AVWRKZWQTYIKIY-UHFFFAOYSA-N ureidocarboxylic acid Natural products NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical group 0.000 claims description 2
- 150000003462 sulfoxides Chemical group 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- ALJYEHUPOPFBCG-UHFFFAOYSA-N nitrophosphonic acid Chemical group OP(O)(=O)[N+]([O-])=O ALJYEHUPOPFBCG-UHFFFAOYSA-N 0.000 claims 1
- 239000004922 lacquer Substances 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 229920002635 polyurethane Polymers 0.000 abstract description 12
- 238000004383 yellowing Methods 0.000 abstract description 9
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229940043232 butyl acetate Drugs 0.000 description 7
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 208000028626 extracranial carotid artery aneurysm Diseases 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- TZLCYBNPPUAZAT-UHFFFAOYSA-N 1-isocyanato-1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)(N=C=O)C1 TZLCYBNPPUAZAT-UHFFFAOYSA-N 0.000 description 2
- DLGUAUVHTOCKTB-UHFFFAOYSA-N 1-isocyanatononane Chemical class CCCCCCCCCN=C=O DLGUAUVHTOCKTB-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000009161 Espostoa lanata Nutrition 0.000 description 2
- 240000001624 Espostoa lanata Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ZNQDRPWGEMAHMQ-UHFFFAOYSA-N N(=C=O)C1=C(C(=C(C(=O)O)C=C1)C)C(=O)O Chemical compound N(=C=O)C1=C(C(=C(C(=O)O)C=C1)C)C(=O)O ZNQDRPWGEMAHMQ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000012628 flowing agent Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002650 habitual effect Effects 0.000 description 2
- 235000015220 hamburgers Nutrition 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- ZAXXZBQODQDCOW-UHFFFAOYSA-N 1-methoxypropyl acetate Chemical compound CCC(OC)OC(C)=O ZAXXZBQODQDCOW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- OPSIPADNUJORFA-UHFFFAOYSA-N 2-ethylhexanoic acid lanthanum Chemical compound [La].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O OPSIPADNUJORFA-UHFFFAOYSA-N 0.000 description 1
- DJSWDXUOSQTQCP-UHFFFAOYSA-N 2-ethylhexanoic acid;titanium Chemical compound [Ti].CCCCC(CC)C(O)=O DJSWDXUOSQTQCP-UHFFFAOYSA-N 0.000 description 1
- DWQHHFSPGQRLMB-UHFFFAOYSA-N 2-ethylhexanoic acid;yttrium Chemical compound [Y].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O DWQHHFSPGQRLMB-UHFFFAOYSA-N 0.000 description 1
- HBHXRPHNNKAWQL-UHFFFAOYSA-N 2-ethylhexanoic acid;zirconium Chemical compound [Zr].CCCCC(CC)C(O)=O HBHXRPHNNKAWQL-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- 101100518161 Arabidopsis thaliana DIN4 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Chemical group 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZLDNZVKBVVPZNI-UHFFFAOYSA-N [Zn].CC(C(C(=O)O)(C)C)(CCCC(=O)O)C Chemical compound [Zn].CC(C(C(=O)O)(C)C)(CCCC(=O)O)C ZLDNZVKBVVPZNI-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种可用以制取泛黄值减少的高档、无分离物涂料或喷漆涂料的新封端多异氰酸酯、其生产方法及其在单组分聚氨酯体系中的应用,特别是在汽车头二道混合底漆作为交联剂的应用。
Description
技术领域
本发明涉及新的封端多异氰酸酯、其制备方法及其在聚氨酯体系中的应用。
对多异氰酸酯实施封端以便将其异氰酸酯基团暂时保护起来,是早就知道的程序,例如在Houben Weyl,《有机化学方法》XIV/2,pp.61~70即有描述。含有封端多异氰酸酯的可硬化组合物例如用于聚氨酯漆中,尤其是用于单组分(1K)聚氨酯体系中。
单组分(1K)聚氨酯体系广泛应用于工业烘漆领域如汽车涂层和卷材涂层的大规模生产,并以其非常好的漆膜性能,如耐化学侵蚀、抗划伤和耐风蚀为特征。此类漆膜是通过任选地在适当催化剂存在下,借助多元醇,封端多异氰酸酯的热活化(通过烘烤过程)实现硬化的。有关原则上适合这里使用的封端剂的综述例如可见诸于Wicks等人,《有机涂料进展》1975,3,pp.73~79,1981,9,pp.3~28和1999,36,pp.148~172。
要用于汽车涂料领域,封端多异氰酸酯必须可在140℃的最高烘烤温度下交联,且必须在烘烤过程中仅表现出非常轻微的泛黄,优选不泛黄。烘烤温度主要通过封端多异氰酸酯的反应性来控制。
大多数烘干体系,例如,蜜胺甲醛和脲-甲醛树脂,特征在于硬化期间释放挥发性组分,因此增加了VOC(挥发性有机化合物)值。
再有,一定比例的封端剂留在形成的漆膜内并对其性能产生负面影响。由于这些封端剂的残留,诸如抗划伤和耐酸之类的单组分漆膜的性能不能与所谓双组分(2C)聚氨酯漆涂料的漆膜相匹敌(例如,T.Engbert,E.,E.Jürgens,《Farbe&Lack》,Curt R.Vincentz出版社,汉诺威10/1995)。另外,封端剂从漆膜中的分离及其以气体形式的逸出会导致在漆膜中气泡的生成。有时可能必须随后对放出的封端剂实施焚烧。
以丙二酸二乙酯封端的异氰酸酯近来被主要用于,90℃~120℃范围内的特别低的烘烤温度(例如,EP-A 10947531)。不同于利用杂环N化合物如己内酰胺或丁酮肟的封端程序,此种封端剂在此种情况下不是完整地分裂出去,而是在以丙二酸二乙酯封端的异氰酸酯上引起酯交换反应。在该酯交换期间分离出乙醇。该方法之所以可用于较低烘烤温度是因为,该第二、相邻的酯官能团是活化的酯。此种方法的缺点是,像这样的体系,由于其活泼的酯键会迅速断裂故对酸的作用极其敏感。因此,此类产物的应用可能性受到限制。
本发明的目的是提供一种新的封端多异氰酸酯体系,它反应时不分离出封端剂,即,不放出气体,并且可在低温下发生交联。本发明的目的还在于,此种封端多异氰酸酯体系在常温下贮存应保持稳定,而且特别是与适当多元醇组分相配合,它们适合用于生产单组分烤漆。
令人惊奇的是,现已发现,具有活化环酮,特别是环戊酮-2-羧甲基酯基本结构的酸性CH化合物封端多异氰酸酯特别适合用来获得泛黄倾向减少且不产气的涂料。
本发明涉及含至少两个异氰酸酯基团的有机多异氰酸酯,其异氰酸酯基团被通式(I)的酸性CH环酮封端,
其中
X是吸电子基团,
R1和R2彼此独立地代表基团氢、C1~C20(环)烷基、C6~C24芳基、C1~C20(环)烷基酯或酰胺、C6~C24芳基酯或酰胺,或者混合的含1~24个碳原子的脂族/芳族基团,它们也可构成4~8元环部分,
n是一个0~5的整数,
并且其封端异氰酸酯基团(按NCO计)含量占总量的0.1~20wt%。
优选封端异氰酸酯基团(按NCO计)含量为0.1~15.6wt%。封端异氰酸酯基团(按NCO计)含量是尤其优选为0.1~14wt%。可任选实施对多异氰酸酯的部分封端;于是,未封端的异氰酸酯基团可用于进一步的反应。就典型而言,所有异氰酸酯基团全部被封端。
吸电子基团X可包含任何导致α-末端氢表现出酸性CH特性的取代基。该取代基可为酯基团、酰胺基团、亚砜基团、砜基团、硝基基团、膦酸酯基团、腈基团、异腈基团、多卤代烷基基团、卤素如氟、氯或羰基基团。优选腈和酯基团,尤其优选羧酸甲酯和羧酸乙酯基团。
通式(I)的化合物,其环任选地含有杂原子如氧、硫或氮原子者,也适合。
通式(I)活化环酮的环的大小优选为5(n=1)或6(n=2)。
优选的通式(I)化合物包括环戊酮-2-羧甲基酯和-羧乙基酯、环戊酮-2-羧酸腈、环己酮-2-羧甲基酯和-羧乙基酯,或者环戊酮-2-羰基甲基。尤其优选环戊酮-2-羧甲基酯和-羧乙基酯乃至环己酮-2-羧甲基酯和-羧乙基酯。环戊酮体系可通过己二酸二甲酯的或己二酸二乙酯的迪克曼缩合方便地以工业规模制取。环己酮-2-羧甲基酯可通过水杨酸甲酯的氢化获得。
待封端的多异氰酸酯可以是任何适合用于含活性氢化合物的交联反应的有机多异氰酸酯,即,含有至少两个异氰酸酯基团的脂族多异氰酸酯,包括环脂族多异氰酸酯,乃至芳族和杂环多异氰酸酯,以及它们的混合物。多异氰酸酯的典型例子包括,脂族异氰酸酯如二-或三异氰酸酯,例如,丁烷二异氰酸酯(BDI)、戊烷二异氰酸酯、己烷二异氰酸酯(HDI)、4-异氰酸根合甲基-1,8-辛烷二异氰酸酯(三异氰酸根合壬烷,TIN),或环状体系如4,4’-亚甲基-双(环己基异氰酸酯)( W,拜尔公司,Leverkusen)、3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基-环己烷(IPDI),乃至ω,ω’-二异氰酸根合-1,3-二甲基环己烷(H6XDI)。芳族多异氰酸酯的例子包括1,5-萘二异氰酸酯、二异氰酸根合-二苯甲烷(MDI)或粗MDI、二异氰酸根合甲基苯(TDI),特别是其2,4-和2,6-异构体以及这两种异构体的工业混合物,乃至1,3-双(异氰酸根合甲基)苯(XDI)。
也非常适合的多异氰酸酯是那些由二-或三异氰酸酯自身通过其异氰酸酯基团起反应制取的多异氰酸脂,例如,脲二酮(uretdione)或碳二亚胺化合物,或者例如通过三个异氰酸酯基团的反应生成的异氰脲酸酯或亚氨基噁二嗪二酮。多异氰酸酯还可包含含有缩二脲、脲基甲酸酯和酰基脲结构要素的单体二-和/或三异氰酸酯和/或低聚多异氰酸酯、具有低单体含量的或部分改性的单体二-或三异氰酸酯,乃至上述多异氰酸酯的任意混合物。
每分子平均含有多于1个异氰酸酯基团的多异氰酸酯预聚物也非常合适。这些预聚物可通过摩尔过量的上述多异氰酸酯之一,与每分子含至少两个例如以羟基基团形式的活性氢,有机材料之间的初步反应来制取。
优选的多异氰酸酯是那些含有脲二酮、异氰脲酸酯、亚氨基噁二嗪二酮、酰基脲、缩二脲或脲基甲酸酯结构的多异氰酸酯,例如,基于以下化合物的那些多异氰酸酯:丁烷二异氰酸酯(BDI)、戊烷二异氰酸酯、己烷二异氰酸酯(HDI)、4-异氰酸根合甲基-1,8-辛烷二异氰酸酯(三异氰酸根合壬烷,TIN)或环状体系,例如,4,4’-亚甲基双(环己基异氰酸酯)( W,拜尔公司,Leverkusen)、3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基环己烷(IPDI),乃至ω,ω’-二异氰酸根合-1,3-二甲基环己烷(H6XDI)。芳族多异氰酸酯的例子包括1,5-萘二异氰酸酯、二异氰酸根合-二苯甲烷(MDI)或粗MDI、二异氰酸根合甲基苯(TDI),特别是其2,4-和2,6-异构体以及这两种异构体的工业混合物,乃至1,3-双(异氰酸根合甲基)苯(XDI)。
特别优选的多异氰酸酯是那些基于己烷二异氰酸酯(HDI),基于4,4’-亚甲基-双(环己基异氰酸酯)或3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基环己烷(IPDI)的多异氰酸酯。
本发明还涉及生产本发明封端有机多异氰酸酯的方法,其特征在于,让多异氰酸酯与通式(I)的酸性CH环酮在催化剂存在下进行反应,其中,每异氰酸酯基团当量待封端多异氰酸酯使用0.8~1.2mol通式(I)的环酮。
其中
X是吸电子基团,
R1和R2彼此独立地代表基团氢、C1~C20(环)烷基、C6~C24芳基、C1~C20(环)烷基酯或酰胺、C6~C24芳基酯或酰胺,或者混合的含1~24个碳原子的脂族/芳族基团,它们也可构成4~8元环部分,并且
n是一个0~5的整数,
1异氰酸酯基团当量待封端多异氰酸酯优选与1当量封端剂起反应。
碱金属和碱土金属碱,例如,粉末状碳酸钠(纯碱)合适作催化剂。视所用环酮而定,也可使用磷酸三钠或Dabco(1,4-二氮杂二环[2.2.2]辛烷)。副族II金属的碳酸盐也适合。优选使用碳酸钠或碳酸钾。另外,环酮与异氰酸酯的反应也可在锌盐催化剂的存在下进行。特别优选采用2-乙基己酸锌的反应。也可用催化剂混合物。
在实施本发明方法时针对所用多异氰酸酯加入0.05~10wt%,优选0.1~3wt%催化剂。最优选使用0.2~1wt%催化剂。
反应可在室温或者在最高140℃的较高温度进行。优选40~90℃的温度范围,特别优选15℃~90℃。
封端反应可在无溶剂或者在适当溶剂存在下进行。合适的溶剂包括惯用漆用溶剂,例如,乙酸丁酯、乙酸甲氧基丙酯或Exxon-Chemie(Esso(德国)公司,汉堡)供应的溶剂石脑油作为含芳族化合物的溶剂,以及上述溶剂的混合物。封端反应优选在上述溶剂中进行,其中固体含量应调节在10~90%之间。
除了按照本发明使用的通式(I)环酮之外,任何封端剂的混合物均可在本发明方法中配合使用,以达到每种情况所要求的漆性能,其中通式(I)化合物的比例至少是30wt%,优选50wt%,最优选100wt%。
最后,本发明还涉及生产1-K PUR(单组分聚氨酯)烘漆的方法,其特征在于,本发明有机多异氰酸酯被用作有机多羟基化合物的交联组分。
本发明封端多异氰酸酯的特征在于,配合适当有机多羟基化合物并在适当催化剂存在下,它们在110~140℃,优选120~140℃的温度和15~30min的烘烤时间内硬化。烘烤时间尤其取决于催化剂的用量。烘烤优选在120~140℃的温度进行30min的时间。
若将本发明封端多异氰酸酯用于生产卷材涂漆,这种封端多异氰酸酯在最长烘烤时间为2分钟下硬化,优选烘烤5~35秒。炉温为300~400℃。烘烤条件当然取决于所用材料以及待涂金属板材的硬度。炉温一般最低为180℃和最高260℃PMT。优选温度范围为210℃~245℃PMT。特别优选温度范围为216℃~241℃PMT。此外,烘烤漆膜的漆技术性能,如在一定温度的MEK(甲乙酮)抗溶剂性、硬度和弹性,还取决于所用催化剂的量。优选于232℃烘烤38秒。在216℃烘烤也是可能的。在基质为铝时烘烤33秒即可。最佳特定条件可以专业技术人员常用的方法用定位预试验确定,而在应用时,卷材涂漆炉的温度用热感器(Sensitivland)加以调控。
适合交联用的催化剂例如有DBTL(二月桂二丁基锡)、2-乙基己酸钛、四异丙醇钛及其它常用钛(IV)化合物、2-乙基己酸锆及其它常用锆(IV)化合物、三乙酸铝、三氟甲烷磺酸钪、2-乙基己酸钇、三氟甲烷磺酸钇、2-乙基己酸镧、三氟甲烷磺酸镧、2-乙基己酸钴、2-乙基己酸酮、三氟甲烷磺酸铟、乙酰乙酸镓、乙酰乙酸镍、2-乙基己酸锂、三氟甲烷磺酸锂、2-乙基己酸钠、乙酸钠、三氟甲烷磺酸钠、2-乙基己酸镁、三氟甲烷磺酸镁、2-乙基己酸钙、三氟甲烷磺酸镁、2-乙基己酸钙、三氟甲烷磺酸钙、2-乙基己酸锌、二硫代氨基甲酸锌、乙酰乙酸锌、四甲基庚二酸锌、水杨酸锌、氯化锌及其它常用锌(II)化合物、2-乙基己酸铋及乙酸铋。优选的催化剂为锌化合物和铋化合物,特别优选2-乙基己酸锌和2-乙基己酸铋。
适合该使用目的的多羟基化合物乃至有关此种类型烤漆的生产和应用详细情况可参见文献例如DE-A 19 738 497或EP-A 0 159 117。本发明产品的最优选应用领域是将其用作汽车头二道混合底漆的交联剂。
一种泛黄值减少的高档、无分离物涂层或漆涂层,可采用本发明封端多异氰酸酯制取。
另外,本发明封端多异氰酸酯可用二-或多胺硬化。该反应优选在室温进行。它可用于生产漆涂层或工件。
生产卷材涂层可用聚酯多元醇、聚碳酸酯和聚酰化多元醇。原则上讲具有足够高OH含量的粘合剂都可使用。
*)拜尔公司产品,Leverkusen,DE
作了上述组分,本发明的粘合剂还可含有其它稳定性添加剂,例如HALS胺或溶剂以及可高达5wt%的OH-功能性酰肼化合物(以成品漆固体物计)。其它添加剂还包括例如CAB(乙酸丁酸纤维素)以及 4F(流动剂(Verlaufmittel)和去泡剂)。
可添加已在EP-A 0 829 500中提及的具有以下通式(II)
的酰肼水合物与2摩尔丙烯碳酸酯的加成物。
实施例
使用的多异氰酸酯是HDI多异氰酸酯,其具有异氰脲酸酯结构、NCO含量21.8%,粘度3200mPa.s( N3300,拜尔公司,Leverkusen)。
作为封端剂使用的环戊酮-2-羧甲基酯和环己酮-2-羧甲基酯是从Fluka公司定购,不经进一步提纯直接使用的。
以酸性α-环酮封端的多异氰酸酯的制备
实例1
将58.5g(0.3当量)溶于81ml乙酸丁酯中的N3300溶液在剧烈搅拌下缓慢加于溶于20ml乙酸丁酯的环戊酮-2-羧甲基酯(42.7g,0.3当量)的溶液。加入1.02g2-乙基己酸锌作为催化剂。将批料加热至50℃(约8h)直至NCO值测定得出约0.2%的数值。理论封端的NCO含量是6.2%。
实例2
将42.6克(0.25当量) N3300的71.4mL乙酸丁酯溶液在剧烈搅拌下缓慢加入到环己酮-2-羧乙基酯(42.6g,0.25当量)溶于20mL乙酸丁酯的溶液中。加入0.9g2-乙基己酸锌作为催化剂。将批料加热至80℃直至NCO值测定得出约0.3%的数值(约6h后)。理论封端的NCO含量是5.75%。
本发明聚氨酯漆的制备
下表所列多异氰酸酯按照下面所列的配方以化学计算量与多元醇一起加工制成清漆,其中加入惯用添加剂 OL 17(拜尔公司,Leverkusen)(流动促进剂)、0.1%固体,相对于固体基料的粘合剂而言)以及(Monsanto公司,Solutia公司,USA;0.01%固体,相对于固体基料的粘合剂而言)。
实例3
漆配方A
N3300(拜尔公司,Leverkusen),以环戊酮-2-羧甲基酯封端(以大约50%在乙酸丁酯中的溶液形式供应;封端的NCO含量:6.2%)(SN=溶剂石脑油,MPA=乙酸甲氧基丙酯,BA=乙酸丁酯):
封堵的NCO/OH比:1.0,
固体含量:约45%,
催化剂含量:1.5%(固体,相对于固体基料的漆料而言)
该体系仅显示非常轻微的泛黄。该体系也可在NCO/OH比为1:1.5时成功地使用。
漆配方B(对比例)
烘烤条件:30min,140℃
就含溶剂的漆而论,即便在较低的烘烤温度下,该体系也表现出明显的发黄。本体系在140~160℃的Δb值是3.2,因此比施涂到含白色溶剂的底漆上仅显示轻微泛黄的体系(例如,二甲基吡唑)高出约3倍。
过度烘烤所致泛黄的测定:漆在140℃烘烤30min后,采用所谓CIELAB方法做第一次颜色测定。按此方式测定得到的正b值越高,表明清漆变得越黄。随后,在160℃过度烘烤30min。然后测定变黄着色的增加,即根据CIELAB色系的所谓Δb值(DIN 6174,“按照CIELAB公式的车身颜色分色的比色测定”(01,79版)。对于不泛黄的清漆,该数值应尽可能接近0。
卷材涂层应用的实施例
原材料:封端多异氰酸酯
以酸性α-环酮封端的多异氰酸酯的制备
封端多异氰酸酯A:
将0.17g 2-乙基己锌(0.05wt%)作为催化剂加入到193.5g(1当量) N3300溶液中,后者溶于14g乙酸甲氧基丙基酯(8份)和29.9g二甲苯(17份)中(共计为溶液的70%)。在氮气下发生下述反应。在这种混合物充分搅匀后,小心地滴加156.2g(1当量)环戊酮-2-羧基乙酯(蒸馏过)。此间反应温度不得超过40℃。滴加完这种酯后于40℃继续搅拌一直到达到NCO值为零(约为6小时后)。封端理论NCO含量为8.3%。然后用(以固体物计为)7%的2-丁酮调至所希望的粘度。接着再加以固体物计为2.5%的 770DF(8.7g)。所配制的多异氰酸是具有异氰脲酸酯结构的HDI多异氰酸酯,其NCO含量为21.8%,粘度为3000mPas( N3300,拜尔公司,Leverkwsen)。
封端多异氰酸酯B:
3 当量(580.5g) N3300和1当量(353g)Z4470在氮气下溶于415g二甲苯中(反应后70%的混合液)。将1.45g(0.1wt%)2-乙基己酸锌作为催化剂加入该混合液。待将这种混合物混合均匀后,将4当量(624.8g)环戊酮-2-羧基乙酯小心地滴加进去。此间反应温度不得超过40℃。滴加完这种酯后于40℃继续搅拌,一直到NCO值接近于零(约12小时)。这样封端NCO含量为8.1%。反应结束后再添加101.7g 2-丁醇(以固体物计为7%)和29g(以固体物计为2%) 770DF。所配制多异氰酸酯是一种具有异氰脲酸酯结构的HDI多异氰酸酯,其NCO含量为21.8%,粘度为3000mPs,( N3300,拜尔公司,Leverkusen)和一种在IPDI基础上制成的具有异氰脲酸酯结构的多异氰酸酯(NCO含量为11.9%,粘度为2000mPs, Z4470,拜尔公司,Leverkwsen)的混合物。
封端多异氰酸酯C:
0.9当量(174.2g) N3300和0.1当量(29g)W-三聚物在氮气下溶于二甲苯中(反应后70%的混合液)。将0.351g(0.1wt%)2-乙基己酸锌作为催化剂加入该混合液。待这种混合物搅拌均匀后,将1当量(156.2g)环戊酮-2-羧基乙酯小心地滴加进去。此间反应温度不得超过40℃。滴加酯完毕后于40℃继续搅拌,一直到NCO值接近于零(约12小时)。封端NCO含量为8.16%。反应结束后再添加7g(以固体物计为2%)Tinuvin 770DF。这样配制约多异氰酸酯是一种具有异氰脲酸酯结构的HDI多异氰酸酯,其NCO含量为21.8%、粘度为3000mPas,( N3300,拜尔公司,Leverkusen)和一种在W基础上制成的具有异氰脲酸酯结构的多异氰酸酯的混合物(13.5% N3300、三聚物化程度20%,NCO含量14.5%,65%固体物质(溶于二甲苯/乙酸甲氧基丙基酯))。
所用封端剂环戊酮-2-羧基乙酯购自Fluka公司。
作比较用的封端多异氰酸酯:
BL3175(拜尔公司),在六甲撑二异氰酸酯基础上制得的交联烘烤尿烷树脂,75%溶于溶剂石油脑,粘度约3300mPas,NCO含量(封端的)约为11.1%,封端剂丁酮肟。
BL3370(拜尔公司),脂族交联烘烤尿烷树脂,约70%溶于乙酸1-甲氧基丙基酯2-(MPA),粘度约3500,1200mPas,NCO含量(封端的)约为8.9%,封端剂二异丙胺。
所用多元醇:见下表。
本发明聚氨酯漆的制备
本发明的漆的生产是按照封端异氰酸酯组分生产规范描述的。
A=多异氰酸酯A,B=多异氰酸酯B,C=多异氰酸酯C
参数
附注 (4+5)CAB和 4F组合用来除气和流动。
供应商 (1) Kronos International INC,Leverkusen
(3) Brenntag,Mülheim/Ruhr
(4) BASF AG,Ludwigshafen
(5) Krahn Chemie,Hamburg
所用原料
1665,在间苯二酸/己二酸/NPG/丙基乙二醇基础上制得的无油、饱和聚酯,拜尔公司,Leverkusen,OH含量:在65%的供货溶于溶剂石油脑100/异丁醇31.5:3.5条件下为1.7%。
CAB(乙酸丁酸纤维素)供应商:Krahn Chemie,汉堡;生产厂商:Eastman Kingsport USA;CAB 531-1(丁酰含量约为53%,羟基含量1.7%可忽略不计)
白色值的测定
ASTM E313,白色指数
按照Berger法测定白色度(无DIN)
白色度=Ry+3(Rz-Rx)
DIN6167黄色指数按照下式计算:
X,Y+Z=DIN 5033的标准色值
a=红/绿轴*
b=蓝/黄轴**
MEK稳定性测定
测定方法的描述(根据ECCA-T11以及DIN EN ISO 2812-1和DINEN 12720):
MEK摩擦试验是一种检验漆膜最终硬化程度的快速检验法。为此一个对漆膜具有恒定压力的并且用MEK浸泡过的棉球在漆膜上来回移动。
仪器/辅助工具:天平(Bizerba牌),100g、1Kg和2kg的砝码
实施:
对涂层厚达20μm施加1kg反压力,对20μm以上的涂层施加2kg反压力。
借助于薄膜夹和防滑薄膜将待试金属薄板固定在天平的盘上。用100g的砝码和皮重平衡器(Taraausgleich)校正天平。一个用MEK浸泡过的棉球向漆膜施加所选测试压力来回移动,直到漆膜被破坏。
分析:
在试验报告中已列出直到涂层破坏的双冲程数字,其中最大的双冲程数字是100。在任意完成100次双冲程后,鉴于漆膜的改变(无光泽、变软)漆膜变形(abgemustert)。
T-bend试验的测定
根据ECCA T7(ECCA:欧洲卷材漆协会)进行方法描述:
目的:
该方法描述了测定有机涂层在180°曲度抗裂纹形成的抗力。
原理:
在这种试验中样品要在1~2秒内与轧向平行弯曲180°,在此过程中涂层处于外侧。必须弯曲到使金属薄板之间发生接触,以保证达到均匀的弯曲度。使样品发生无裂纹弯曲的最小弯曲半径决定180°曲度的抗力。在此过程中要用粘合带对每次弯曲后的附着现象进行检验。
器具:
可用来实施本方法的器具有一个螺旋式虎钳和一套保护夹具。
准备工作:
待测样品在实验室室温和空气湿度中存放至少24小时。测试在同样条件下进行。
如果规定了更详细的条件或在仲裁情况下,则应注意ISO 3270-1984的说明,即温度为23±2℃和相对空气湿度为50±5%。
程序:
沿轧制方向裁下一条约2cm宽的金属薄带。在1~2秒内将此金属薄带与轧向平行弯曲180°,在此过程中涂层处于外侧。然后用螺旋式虎钳将其紧紧压紧。
用20倍的放大镜检查弯曲棱。然后对附着现象进行三次挤压,并且撕下一片粘合带进行检查。
这种0T曲度的变形(Abmusterung),用R表示裂纹和用H表示附着,用0-5进行评估,0是最好的值,5是最差的值。
然后使该金属薄板来后弯曲直到裂纹形成和出现附着现象时达到数值0。
检验最迟在3.0T结束。
再拉扯稳定性
这种变形的T-bend金属薄带于30分钟加热至100℃,然后再拉扯变形。
漆的制备:
本试验按照标准配方(标准配方RR6830)在白色卷材涂用的涂盖清漆中进行。这首先要用无油饱和聚酯按下述珠磨配方制备硬磨材料:
7.8份 溶剂200S
22.3份 白色颜料Kronos 2330
研磨材料用2mm硅石英珠分散开。
研磨材料通过过筛与玻璃珠分开。
在搅拌下添加其余的漆组分。
11.9份 封端多异氰酸酯*)
用刮板将漆涂于铬酸钝化的铝板(1mm厚)上。铝板涂漆后立即放在转盘上于Aalborg炉中烘烤。
PMT210℃,于350℃炉温烘烤30秒
PMT216℃,于350℃炉温烘烤33秒
PMT224℃,于350℃炉温烘烤35秒
PMT232℃,于350℃炉温烘烤38秒
PMT>254℃,于350℃炉温烘烤50秒
干涂层厚20-22μm。
综上所述,本发明提供的部分技术方案如下:
1.一种含至少两个异氰酸酯基团的有机多异氰酸酯,其异氰酸酯基团被通式(I)的酸性CH环酮封端,
其中
X是吸电子基团,
其中所述吸电子基团X选自酯、酰胺、亚砜、砜、硝基、膦酸酯、腈、异腈、多卤代烷基基团、氟、氯或羰基基团;
R1和R2彼此独立地代表基团氢、C1~C20烷基、C1~C20环烷基、C6~C24芳基、C1~C20烷基酯或-酰胺、C1~C20环烷基酯或-酰胺、C6~C24芳基酯或-酰胺,或者混合的含1~24个碳原子的脂族/芳族基团,它们也可构成4~8元环部分,
n是一个0~5的整数,
并且其封端异氰酸酯基团,按NCO计的含量占有机多异氰酸酯总量的0.1~20wt%。
2.技术方案1的有机多异氰酸酯,其特征在于,通式(I)的酸性CH环酮包括环戊酮-2-羧甲基酯和-羧乙基酯,环戊酮-2-羧酸腈、环己酮-2-羧甲基酯和-羧乙基酯或环戊酮-2-羰基甲基。
3.技术方案1的有机多异氰酸酯,其特征在于,通式(I)的酸性CH环酮包括环戊酮-2-羧甲基酯和-羧乙基酯,环己酮-2-羧甲基酯和-羧乙基酯。
4.一种生产技术方案1的有机多异氰酸酯的方法,其特征在于,让多异氰酸酯与技术方案1所定义的通式(I)的酸性CH环酮在催化剂存在下进行反应,其中待封端的多异氰酸酯的每异氰酸酯基团当量使用0.8~1.2mol技术方案1所定义的通式(I)的环酮。
5.技术方案4的方法,其特征在于,有机多异氰酸酯含有脲二酮、异氰脲酸酯、亚氨基噁二嗪二酮、酰基脲、缩二脲或脲基甲酸酯结构。
6.技术方案4的方法,其特征在于,
·碱金属-、碱土金属-碱,
·路易斯酸
用作催化剂。
7.技术方案6的方法,其中所述路易斯酸为锌盐。
8.聚氨酯烤漆,其含有技术方案1的有机多异氰酸酯。
9.技术方案8的聚氨酯烤漆,其为单组分聚氨酯-烤漆。
10.技术方案1的有机多异氰酸酯用于填充剂的用途。
11.技术方案1的有机多异氰酸酯用于卷材涂层的用途。
12.含有技术方案1的封端有机多异氰酸酯的涂料或聚氨酯漆。
Claims (12)
2.权利要求1的有机多异氰酸酯,其特征在于,通式(I)的酸性CH环酮是环戊酮-2-羧甲基酯或-羧乙基酯,环戊酮-2-羧酸腈、环己酮-2-羧甲基酯或-羧乙基酯或环戊酮-2-羰基甲基。
3.权利要求1的有机多异氰酸酯,其特征在于,通式(I)的酸性CH环酮是环戊酮-2-羧甲基酯或-羧乙基酯,环己酮-2-羧甲基酯或-羧乙基酯。
4.一种生产权利要求1的有机多异氰酸酯的方法,其特征在于,让多异氰酸酯与权利要求1所定义的通式(I)的酸性CH环酮在催化剂存在下进行反应,其中待封端的多异氰酸酯的每异氰酸酯基团当量使用0.8~1.2mol权利要求1所定义的通式(I)的环酮。
5.权利要求4的方法,其特征在于,有机多异氰酸酯含有脲二酮、异氰脲酸酯、亚氨基噁二嗪二酮、酰基脲、缩二脲或脲基甲酸酯结构。
6.权利要求4的方法,其特征在于,
碱金属-或碱土金属-碱,或
路易斯酸,
用作催化剂。
7.权利要求6的方法,其中所述路易斯酸为锌盐。
8.聚氨酯烤漆,其含有权利要求1的有机多异氰酸酯。
9.权利要求8的聚氨酯烤漆,其为单组分聚氨酯-烤漆。
10.权利要求1的有机多异氰酸酯用于填充剂的用途。
11.权利要求1的有机多异氰酸酯用于卷材涂层的用途。
12.含有权利要求1的封端有机多异氰酸酯的涂料或聚氨酯烤漆。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10132016.7 | 2001-07-03 | ||
DE10132016A DE10132016A1 (de) | 2001-07-03 | 2001-07-03 | Cyclische Ketone als Blockierungsmittel |
DE10226926.2 | 2002-06-17 | ||
DE2002126926 DE10226926A1 (de) | 2002-06-17 | 2002-06-17 | Blockierte Polyisocyanate |
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CN1524099A CN1524099A (zh) | 2004-08-25 |
CN100467511C true CN100467511C (zh) | 2009-03-11 |
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CNB028135504A Expired - Fee Related CN100467511C (zh) | 2001-07-03 | 2002-07-03 | 作为封端剂用的环酮 |
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EP (1) | EP1404737A1 (zh) |
JP (1) | JP4118803B2 (zh) |
KR (1) | KR100875808B1 (zh) |
CN (1) | CN100467511C (zh) |
BR (1) | BR0210799A (zh) |
CA (1) | CA2451744A1 (zh) |
HK (1) | HK1069181A1 (zh) |
HU (1) | HU226903B1 (zh) |
MX (1) | MXPA03011808A (zh) |
NZ (1) | NZ530396A (zh) |
PL (1) | PL367450A1 (zh) |
WO (1) | WO2003004545A1 (zh) |
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DE10260298A1 (de) * | 2002-12-20 | 2004-07-01 | Bayer Ag | Hydrophilierte blockierte Polysocyanate |
DE10260300A1 (de) * | 2002-12-20 | 2004-07-01 | Bayer Ag | Abspalterfreie Pulverlackvernetzer |
DE10260270A1 (de) * | 2002-12-20 | 2004-07-01 | Bayer Ag | Hydrophile Polyurethan-Polyharnstoff-Dispersion |
DE10260269A1 (de) * | 2002-12-20 | 2004-07-01 | Bayer Ag | Neue Dual Cure-Systeme |
DE10260299A1 (de) * | 2002-12-20 | 2004-07-01 | Bayer Ag | Reaktivsysteme, deren Herstellung und deren Verwendung |
DE10357713A1 (de) | 2003-12-09 | 2005-07-14 | Bayer Materialscience Ag | Beschichtungsmittel |
DE102004043342A1 (de) * | 2004-09-08 | 2006-03-09 | Bayer Materialscience Ag | Blockierte Polyurethan-Prepolymere als Klebstoffe |
US20070031672A1 (en) * | 2005-08-08 | 2007-02-08 | Frank-Rainer Boehm | Wire-coating composition based on new polyester amide imides and polyester amides |
GB2435472A (en) | 2006-02-23 | 2007-08-29 | 3M Innovative Properties Co | Method for forming an article having a decorative surface |
US20090298962A1 (en) * | 2006-09-29 | 2009-12-03 | Katia Studer | Photolatent bases for systems based on blocked isocyanates |
US9006350B2 (en) * | 2006-12-22 | 2015-04-14 | Axalta Coating Systems Ip Co., Llc | Selfbonding enamels based on new polyester amide imides and polyester amides |
JP5274598B2 (ja) | 2011-02-22 | 2013-08-28 | 富士フイルム株式会社 | レーザー彫刻用組成物、レリーフ印刷版原版、レリーフ印刷版の製版方法、及び、レリーフ印刷版 |
EP2813554A3 (en) * | 2013-06-13 | 2015-07-29 | Eczacibasi Yapi Gerecleri Sanayi Ve Ticaret Anonim Sirketi | A mixture/composition for forming non-skid surface, a method for preparing and applying the mixture and the products that this composition is applied on |
CN106572964B (zh) * | 2014-08-05 | 2020-05-19 | 科思创德国股份有限公司 | 用于化妆品组合物的聚氨酯脲溶液 |
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US5071937A (en) * | 1987-12-22 | 1991-12-10 | Mobay Corporation | Coating compositions based on blocked polyisocyanates and sterically hindered aromatic polyamines |
JP3299197B2 (ja) * | 1998-09-30 | 2002-07-08 | 第一工業製薬株式会社 | 熱硬化性水系金属用防錆塗料 |
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- 2002-07-03 EP EP02782451A patent/EP1404737A1/de not_active Withdrawn
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HUP0401289A3 (en) | 2009-03-02 |
CA2451744A1 (en) | 2003-01-16 |
PL367450A1 (en) | 2005-02-21 |
JP4118803B2 (ja) | 2008-07-16 |
KR100875808B1 (ko) | 2008-12-24 |
BR0210799A (pt) | 2004-08-17 |
CN1524099A (zh) | 2004-08-25 |
NZ530396A (en) | 2005-07-29 |
HU226903B1 (en) | 2010-01-28 |
HK1069181A1 (en) | 2005-05-13 |
MXPA03011808A (es) | 2004-07-01 |
JP2004533526A (ja) | 2004-11-04 |
KR20040015326A (ko) | 2004-02-18 |
WO2003004545A1 (de) | 2003-01-16 |
EP1404737A1 (de) | 2004-04-07 |
HUP0401289A2 (hu) | 2004-09-28 |
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