CN116568720A - 具有极低单体含量的非离子亲水化多异氰酸酯 - Google Patents
具有极低单体含量的非离子亲水化多异氰酸酯 Download PDFInfo
- Publication number
- CN116568720A CN116568720A CN202180084200.8A CN202180084200A CN116568720A CN 116568720 A CN116568720 A CN 116568720A CN 202180084200 A CN202180084200 A CN 202180084200A CN 116568720 A CN116568720 A CN 116568720A
- Authority
- CN
- China
- Prior art keywords
- polyisocyanate
- uretdione
- weight
- polyisocyanates
- structures
- 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
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 155
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 155
- 239000000178 monomer Substances 0.000 title description 13
- 238000000034 method Methods 0.000 claims abstract description 51
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 25
- 239000008199 coating composition Substances 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 63
- 229910052698 phosphorus Inorganic materials 0.000 claims description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 47
- 239000011574 phosphorus Substances 0.000 claims description 47
- 229920000570 polyether Polymers 0.000 claims description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 24
- 150000002894 organic compounds Chemical class 0.000 claims description 22
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical compound N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 20
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 20
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 19
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical group O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 claims description 19
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 150000002433 hydrophilic molecules Chemical class 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 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 claims description 4
- 238000000120 microwave digestion Methods 0.000 claims description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 22
- 150000001298 alcohols Chemical class 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003776 cleavage reaction Methods 0.000 description 9
- 230000007017 scission Effects 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 8
- -1 hydrocarbon radical Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002396 Polyurea Polymers 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical compound O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- VTBOTOBFGSVRMA-UHFFFAOYSA-N 1-Methylcyclohexanol Chemical class CC1(O)CCCCC1 VTBOTOBFGSVRMA-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XYYXDARQOHWBPO-UHFFFAOYSA-N 3,5-dimethyl-1h-1,2,4-triazole Chemical compound CC1=NNC(C)=N1 XYYXDARQOHWBPO-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
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- RQINQJTUMGQYOB-UHFFFAOYSA-N 6-methylheptyl dihydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(O)=O RQINQJTUMGQYOB-UHFFFAOYSA-N 0.000 description 1
- IJEFAHUDTLUXDY-UHFFFAOYSA-J 7,7-dimethyloctanoate;zirconium(4+) Chemical compound [Zr+4].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O IJEFAHUDTLUXDY-UHFFFAOYSA-J 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- BHCFVCRRNLIOGM-UHFFFAOYSA-J C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] BHCFVCRRNLIOGM-UHFFFAOYSA-J 0.000 description 1
- ZRQVXQKJGHZTOQ-UHFFFAOYSA-N CCC(C)OP(O)=O Chemical compound CCC(C)OP(O)=O ZRQVXQKJGHZTOQ-UHFFFAOYSA-N 0.000 description 1
- XBEDEUGIOGUZSN-UHFFFAOYSA-N CCCCC(CC)COP(O)=O Chemical compound CCCCC(CC)COP(O)=O XBEDEUGIOGUZSN-UHFFFAOYSA-N 0.000 description 1
- MGJJRXIEFROZLZ-UHFFFAOYSA-N CCCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCCOP(O)=O MGJJRXIEFROZLZ-UHFFFAOYSA-N 0.000 description 1
- ZBEKPPVMYNVMQO-UHFFFAOYSA-N CCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCOP(O)=O ZBEKPPVMYNVMQO-UHFFFAOYSA-N 0.000 description 1
- XJKCIKMIYBWISX-UHFFFAOYSA-N CCCCCCCCOP(O)=O Chemical compound CCCCCCCCOP(O)=O XJKCIKMIYBWISX-UHFFFAOYSA-N 0.000 description 1
- DEVJMJPPUVBPOV-UHFFFAOYSA-N CCCCCCCOP(O)=O Chemical compound CCCCCCCOP(O)=O DEVJMJPPUVBPOV-UHFFFAOYSA-N 0.000 description 1
- OEODWKRQWJHQSK-UHFFFAOYSA-N CCCCCCOP(O)=O Chemical compound CCCCCCOP(O)=O OEODWKRQWJHQSK-UHFFFAOYSA-N 0.000 description 1
- WCJLOEFXANROAO-UHFFFAOYSA-N CCCCOP(O)=O Chemical compound CCCCOP(O)=O WCJLOEFXANROAO-UHFFFAOYSA-N 0.000 description 1
- DEVWEFBXXYMHIL-UHFFFAOYSA-N CCCOP(O)=O Chemical compound CCCOP(O)=O DEVWEFBXXYMHIL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 238000006887 Ullmann reaction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
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- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
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- PYKHKJJMHQLJOH-UHFFFAOYSA-N bis(3-methylbutyl) hydrogen phosphate Chemical compound CC(C)CCOP(O)(=O)OCCC(C)C PYKHKJJMHQLJOH-UHFFFAOYSA-N 0.000 description 1
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical class CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 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 description 1
- OGDSVONAYZTTDA-UHFFFAOYSA-L tert-butyl-dioxido-oxo-$l^{5}-phosphane Chemical compound CC(C)(C)P([O-])([O-])=O OGDSVONAYZTTDA-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- BCHASIUOFGDRIO-UHFFFAOYSA-N trimethylsilyl methanesulfonate Chemical compound C[Si](C)(C)OS(C)(=O)=O BCHASIUOFGDRIO-UHFFFAOYSA-N 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/027—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing urethodione groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及生产具有极低单体二异氰酸酯含量的亲水改性多异氰酸酯的方法、通过所述方法可获得或已获得的多异氰酸酯,及其用于生产聚氨酯塑料的用途。本发明进一步涉及含有所述非离子亲水改性多异氰酸酯的涂料组合物,以及用这些涂料组合物涂覆的基底。
Description
本发明涉及生产具有低单体二异氰酸酯含量的亲水改性多异氰酸酯的方法、通过所述方法可获得或已获得的多异氰酸酯、及其用于生产聚氨酯塑料的用途。本发明进一步涉及含有所述非离子亲水改性多异氰酸酯的涂料组合物,以及用这些涂料组合物涂覆的基底。
水性涂料体系如今作为含溶剂的涂料组合物的环保替代品在各种应用领域中建立牢固的地位。亲水改性的多异氰酸酯在此作为高品质水性涂料的原材料起到特定作用,因为其作为水分散性交联剂组分实现水性双组分聚氨酯(2K-PUR)涂料的配制。
生产水分散性多异氰酸酯的简单廉价的方法是疏水多异氰酸酯与亲水聚醚醇的按比例反应(参见例如EP-A 0 959 087,第2页,第25-46行)。在工业规模下,这种反应通常在大约80℃至130℃的温度下进行以确保经济上可接受的反应时间。
但是,在含有脲二酮结构的多异氰酸酯的亲水化中,在这一温度范围内其热不稳定性变得明显不利,这会导致单体二异氰酸酯的显著增加。
亲水多异氰酸酯未来也将受到欧洲化学品管理局(ECHA)关于处理游离单体二异氰酸酯含量为0.10重量%或更高的物质或混合物施加的限制。为了安全地在商业上用作水性2K PUR涂料中的交联剂组分,因此需要包含少于0.10%单体二异氰酸酯的亲水多异氰酸酯。
EP 3 543 270 A1涉及用于脲二酮分散体的催化剂体系,其中没有描述具有基于固含量计小于0.10重量%的残留单体含量的亲水多异氰酸酯。US 5,252,696 A和EP 0 850896 A1描述了水分散性多异氰酸酯,没有细说例如残留单体含量。WO2016/146474 A1公开了在有机溶剂中存在的含硅烷基团的多异氰酸酯。
EP 3 428 207 A1描述了具有特定比率的脲酮亚胺和亚氨基噁二嗪二酮基团(在每种情况下基于存在的异氰脲酸酯基团计)的亲水多异氰酸酯组合物,由此得到0.20至50摩尔%的脲酮亚胺基团与脲二酮基团的比率。在此,在亲水化反应之前通过加热多异氰酸酯而有意形成脲酮亚胺基团。其缺点在于,必定强制性地存在热不稳定的脲酮亚胺基团并且不能保证单体二异氰酸酯的含量可以可靠地保持在低于0.10重量%。
但是,疏水多异氰酸酯中极少量的脲二酮结构已会在常规条件下与亲水聚醚醇的反应过程中通过逆向裂解导致单体含量升高到明显高于0.10重量%的值,即使如果该疏水多异氰酸酯最初具有小于0.10重量%的二异氰酸酯含量。
因此本发明的目的是提供生产非离子亲水改性多异氰酸酯的新型方法,借此可以使含脲二酮基团和任选脲酮亚胺基团的疏水多异氰酸酯与亲水聚醚醇反应,而没有由于脲二酮裂解和脲酮亚胺裂解使单体二异氰酸酯明显增加到超过0.10重量%。
通过提供下面更详细描述的方法实现这一目的。根据本发明的方法基于令人惊讶的观察结果,即脲二酮裂解和脲酮亚胺裂解以及因此单体二异氰酸酯含量增加的趋势在很大程度上与所用聚醚醇的品质相关。用于多异氰酸酯亲水化的聚醚醇通常通过碱金属催化的环氧烷,特别是环氧乙烷加成到具有至少一个活性氢原子的起始剂分子上制成。在加成反应后,然后通常用无机或有机酸中和碱性催化剂,并从聚醚醇中除去在此形成的盐。现在已经令人惊讶地发现,含脲二酮基团和任选脲酮亚胺基团的多异氰酸酯与用磷酸或磷酸酯中和的亲水聚醚醇的反应导致单体二异氰酸酯的显著增加,而在与无磷聚醚醇或包含小于50ppm磷的聚醚醇的反应中没有观察到脲二酮裂解和脲酮亚胺裂解。
本发明的主题是生产具有基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯含量的亲水改性多异氰酸酯的方法,其包括以下组分的反应
A)至少一种具有脂族、脂环族、芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分,其包含至少脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构,与
B)至少一种非离子亲水有机化合物,其包含至少一个异氰酸酯反应性基团,
其中所述非离子亲水有机化合物B)具有最大50ppm的磷含量,并且基于所述亲水改性多异氰酸酯的组分A)和B)计的总磷含量最大20ppm。
本发明的主题还是非离子亲水改性多异氰酸酯,其包含脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯和最大20ppm的磷,及其作为聚氨酯塑料生产中的起始组分的用途,特别是在使用基于下述粘合剂或粘合剂组分的水性涂料组合物的涂料生产中作为具有对异氰酸酯基团呈反应性的基团的水溶性或水分散性涂料粘合剂或涂料粘合剂组分的交联剂的用途。
根据本发明,术语“包含”或“含有”优选是指“基本由…组成”,特别优选是指“由…组成”。在权利要求书和说明书中提到的进一步实施方案可任意组合,只要上下文没有清楚表明情况相反。
“有机化合物”或“有机基团”含有至少一个含共价碳氢键的单元。
术语“脂族”在此被定义为是指饱和或不饱和的非芳族烃基。
术语“芳脂族”在此被定义为是指由芳族烃基和直接键合至芳族基团的饱和或不饱和烃基组成的烃基。
术语“脂环族”或“环脂族”在此被定义为是指非芳族的任选取代的碳环或杂环化合物或单元。
术语“亲水”在此被定义为化合物的水溶解度为至少500克/升,优选完全可溶于水,术语“疏水”被定义为化合物的水溶解度最大100克/升,优选完全不溶于水,在每种情况下在20℃下测定。
本文所用的“至少一种”是指一种或更多种,例如2、3、4、5、6、7、8、9种或更多种。关于本文所述的化合物的成分,这一数值不涉及分子的绝对数量,而是涉及成分的性质。“至少一种非离子亲水有机化合物”因此被理解为是指,例如,可以包含仅一种类型的此类化合物或两种或更多种不同类型的此类化合物,而非说明各化合物的量。
以格式“x至y”给出的数值范围包括所述值。如果以这种格式给出多个优选数值范围,要理解的是,同样包含由各种端点的组合产生的所有范围。
用于根据本发明的方法的合适的多异氰酸酯A)是通过包含至少脲二酮结构的简单脂族、脂环族、芳脂族和/或芳族二异氰酸酯的改性制成的任何所需多异氰酸酯。
用于生产多异氰酸酯A)的合适二异氰酸酯可通过各种手段获得,例如通过相应的二胺在液相或气相中的光气化或通过无光气途径,例如通过热氨酯裂解。优选的二异氰酸酯是具有脂族、脂环族、芳脂族和/或芳族键合的异氰酸酯基团的分子量范围为140至400的那些,例如1,4-丁烷二异氰酸酯、1,5-戊烷二异氰酸酯(PDI)、1,6-己烷二异氰酸酯(HDI)、2-甲基-1,5-戊烷二异氰酸酯、1,5-二异氰酸根合-2,2-二甲基戊烷、2,2,4-或2,4,4-三甲基-1,6-己烷二异氰酸酯、1,10-癸烷二异氰酸酯、1,3-和1,4-环己烷二异氰酸酯、1,3-和1,4-双(异氰酸根合甲基)环己烷、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)、2,4′-和4,4′--二环己基甲烷二异氰酸酯、1-异氰酸根合-1-甲基-4(3)异氰酸根合甲基环己烷、双(异氰酸根合甲基)降冰片烷、1,3-和1,4-双(异氰酸根合甲基)苯(苯二亚甲基二异氰酸酯,XDI)、1,3-和1,4-双(2-异氰酸根合丙-2-基)苯(四甲基苯二亚甲基二异氰酸酯,TMXDI)、2,4-和2,6-甲苯二异氰酸酯(TDI)、2,4′-和4,4′--二苯甲烷二异氰酸酯(MDI)、1,5-萘二异氰酸酯或至少两种这样的二异氰酸酯的混合物。
除脲二酮结构外,根据本发明的方法中所用的多异氰酸酯A)还可任选包含异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构。
多异氰酸酯A)的生产根据本身已知的方法进行,例如描述在J.Prakt.Chem.336(1994)185-200、DE-A 1 670 666、DE-A 1 954 093、DE-A 2 414 413、DE-A 2 452 532、DE-A 2 641 380、DE-A 3 700 209、DE-A 3 900 053和DE-A 3 928 503,或EP-A 0 336 205、EP-A 0 339 396、EP-A 0 798 299、EP-A 0 986 009、EP-A 0 962 454、EP-A 0 962 455、EP-A 2 785 760、EP-A 2 883 895、EP-A 3 107 922、EP-A 3 107 948和EP-A 3 337 836中。
在这些多异氰酸酯A)的生产中,在实际改性反应后通常接着用于分离出未反应的过量单体二异氰酸酯的进一步工艺步骤。通过本身已知的方法,优选通过在真空下的薄膜蒸馏或通过用对异氰酸酯基团呈惰性的合适溶剂,例如脂族或脂环族烃,如戊烷、己烷、庚烷、环戊烷或环己烷萃取来分离出单体。
根据本发明的方法中优选使用具有小于0.14重量%,优选小于0.12重量%,特别优选小于0.10重量%的单体二异氰酸酯含量的多异氰酸酯A)。根据DIN EN ISO 10283:2007-11通过使用内标的气相色谱法测定残留单体含量。
根据其各自的生产方法,根据本发明的方法中所用的多异氰酸酯组分A)可任选含有最多28ppm,优选最多25ppm,特别优选最多20ppm的量的磷,其例如以滞留的低聚催化剂的形式存在。在本发明中,在微波消解后根据DIN EN ISO 11885:2009-09通过电感耦合等离子体原子发射光谱法(ICP-OES)进行这些磷含量的测定。使用这种方法的磷检出限为<1ppm。
多异氰酸酯A)中存在脲二酮结构,脲二酮结构的含量优选为至少0.6摩尔%,更优选0.8至25摩尔%,特别优选1至20摩尔%,非常特别优选1至15摩尔%,在每种情况下基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%。如果可检测到,多异氰酸酯A)中的脲酮亚胺结构的含量为基于脲二酮结构计小于0.20摩尔%,优选小于0.15摩尔%,特别优选小于0.10摩尔%。
多异氰酸酯A)中存在的脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的含量(摩尔%)由质子解耦13C-NMR谱的积分计算,并在每种情况下基于存在的脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的总和计。多异氰酸酯A)中任选存在的脲酮亚胺结构的含量(摩尔%)同样由质子解耦13C-NMR谱的积分计算,并参考脲二酮结构。在CDCl3中溶解的HDI多异氰酸酯的情况下,各个结构元素具有以下化学位移(以ppm计):脲二酮:157.1;异氰脲酸酯:148.4;亚氨基噁二嗪二酮:147.8、144.3和135.3;脲基甲酸酯:155.7和153.8、缩二脲:155.5;氨基甲酸酯:156.3;噁二嗪三酮:147.8和143.9;脲酮亚胺:158.7和144.6。
合适的多异氰酸酯A)还包括至少两种所述类型的多异氰酸酯的任何所需混合物,其中这些混合物中也可使用完全不含脲二酮结构的多异氰酸酯,只要该混合物在脲二酮和脲酮亚胺结构的含量方面对应于上文对多异氰酸酯A)作出的说明。
优选的多异氰酸酯A)是除脲二酮结构外还含有至少异氰脲酸酯结构的所述类型的那些。
在根据本发明的方法中,如果使用的话,具有芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯优选以基于多异氰酸酯A)的总量计最大20重量%,特别优选最大10重量%的量一同使用。用于根据本发明的方法的特别优选的多异氰酸酯A)是具有仅脂族和/或脂环族键合的异氰酸酯基团的所述类型的那些,其不含脲酮亚胺基团或其中无法检测到脲酮亚胺基团。
非常特别优选的多异氰酸酯A)是基于PDI、HDI、IPDI和/或2,4′-和4,4′--二环己基甲烷二异氰酸酯的那些。
上文作为合适、优选、特别优选和非常特别优选提到的多异氰酸酯A)含有脲二酮结构和任选优选异氰脲酸酯结构,并具有2.3至5.0,优选2.5至4.5的平均NCO官能度和6.0至26.0重量%,优选8.0至25.0重量%,特别优选10.0至24.0重量%的异氰酸酯基团含量。
用于根据本发明的方法的起始化合物B)是具有至少一个异氰酸酯反应性基团并具有最大50ppm的磷含量的任何所需非离子亲水有机化合物。本发明的起始化合物B)优选不包括WO 2016/146474A1中明确提到的对异氰酸酯基团呈反应性的硅烷化合物。
合适的起始化合物B)是例如可以本身已知的方式通过合适的起始剂分子的烷氧基化获得的具有每分子统计平均5至50个环氧乙烷单元的一元或多元聚环氧烷聚醚醇(例如参见Ullmannsder technischen Chemie,第4版,第19卷,VerlagChemie,Weinheim第31—38页)。合适的起始剂分子可包括例如分子量范围32至300的任何所需一元醇或多元醇,例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、异构戊醇、己醇、辛醇和壬醇、正癸醇、正十二烷醇、正十四烷醇、正十六烷醇、正十八烷醇、环己醇、异构甲基环己醇、羟甲基环己烷、3-甲基-3-羟甲基氧杂环丁烷、苄醇、苯酚、异构甲酚、辛基苯酚、壬基苯酚和萘酚、糠醇、四氢糠醇、1,2-乙二醇、1,2-和1,3-丙二醇、异构丁二醇、戊二醇、己二醇、庚二醇和辛二醇、1,2-和1,4-环己二醇、1,4-环己烷二甲醇、4,4′-(1-甲基亚乙基)双环己醇、1,2,3-丙三醇、1,1,1-三羟甲基乙烷、1,2,6-己三醇、1,1,1-三羟甲基丙烷、2,2-双(羟甲基)-1,3-丙二醇或1,3,5-三(2-羟乙基)异氰脲酸酯。
适用于烷氧基化反应的环氧烷尤其是环氧乙烷和环氧丙烷,这些可以任何所需顺序或以混合物的形式用于烷氧基化反应。合适的聚醚醇是纯聚环氧乙烷聚醚醇或混合聚环氧烷聚醚,其环氧烷单元在至少70摩尔%的程度上,优选在至少80摩尔%的程度上由环氧乙烷单元组成。
优选的聚环氧烷聚醚醇B)是使用分子量范围32至150的上述一元醇作为起始剂分子制成的那些。更优选的是,非离子亲水有机化合物B)是具有每分子统计平均5至50个环氧乙烷单元,特别优选5至25个环氧乙烷单元的一元或多元聚环氧烷聚醚醇。特别优选的聚醚醇是具有统计平均5至50,尤其优选5至25个环氧乙烷单元的纯聚乙二醇单甲基醚醇。
非离子亲水化合物B)优选具有4.0至8.0,优选4.5至7.5,特别优选5.0至7.0的作为5%水溶液测得的pH值。
在根据本发明的方法中,非离子亲水化合物B)的用量可以在宽范围内自由选择。在根据本发明的方法中,非离子亲水化合物B)优选以基于所用起始组分A)和B)的总量计最多30重量%,特别优选2重量%至25重量%,非常特别优选5至20重量%,特别是9重量%至17重量%的量使用。
对于本发明至关重要的是,非离子亲水化合物B)具有最大50ppm,优选最大40ppm,特别优选最大30ppm的磷含量,非常特别优选不含可检出的磷,其中在微波消解后根据DINEN ISO 11885:2009-09通过电感耦合等离子体原子发射光谱法(ICP-OES)测定磷含量。使用这种方法的磷检出限为<1ppm。
同样可通过上述ICP-OES方法测定的由组分A)和B)组成的根据本发明的亲水改性多异氰酸酯中的总磷含量最大20ppm,优选3至19ppm,特别优选5至18ppm。
但是,根据本发明的亲水改性多异氰酸酯中的总磷含量也可以由多异氰酸酯组分A)和亲水化合物B)的磷含量以简单的方式计算得到。在总磷含量的计算中,在此还包括为了稳定或中和碱性催化剂残留物而在反应之前和/或期间任选以多异氰酸酯组分A)和/或非离子亲水有机化合物B)的酸性磷化合物的形式加入的磷量。
这样的酸性磷化合物包括例如磷酸、磷酸酯,例如磷酸甲酯、磷酸乙酯、磷酸正丁酯、磷酸正己酯、磷酸2-乙基己酯、磷酸异辛酯、磷酸正十二烷基酯、磷酸二甲酯、磷酸二乙酯、磷酸二正丙酯、磷酸二正丁酯、磷酸二正戊酯、磷酸二异戊酯、磷酸二正癸酯、磷酸二苯酯和磷酸二苄酯,和/或膦酸酯,例如膦酸甲酯、膦酸乙酯、膦酸异丙酯、膦酸正丙酯、膦酸正丁酯、膦酸异丁酯、膦酸仲丁酯、膦酸叔丁酯、膦酸正己酯、膦酸正庚酯、膦酸正辛酯、膦酸正癸酯、膦酸正十二烷基酯、膦酸2-乙基己酯和膦酸2-丙基庚酯。
根据本发明的方法优选不用溶剂进行。但是,任选也可以一同使用对起始组分的反应性基团,特别是对异氰酸酯基团呈惰性的合适溶剂。合适溶剂是例如本身已知的常规涂料溶剂,例如乙酸乙酯、乙酸丁酯、乙二醇单甲基或单乙基醚乙酸酯、乙酸1-甲氧基-2-丙基酯、乙酸3-甲氧基-正丁基酯、丙酮、2-丁酮、4-甲基-2-戊酮、环己酮、甲苯、二甲苯、氯苯、溶剂油(Testbenzin)、例如以溶剂石脑油、 (DeutscheEXXON CHEMICAL GmbH,/>DE)和/>(Deutsche Shell Chemie GmbH,Eschborn,DE)为名商业化可得的较高度取代的芳烃,碳酸酯,如碳酸二甲酯、碳酸二乙酯、碳酸1,2-亚乙酯和碳酸1,2-亚丙酯,内酯如β-丙内酯、γ-丁内酯、ε-己内酯和ε-甲基己内酯,以及如丙二醇二乙酸酯、二乙二醇二甲基醚、二丙二醇二甲基醚、丁基乙二醇乙酸酯、丁基二乙二醇乙酸酯、1,3-二氧戊环、N-甲基吡咯烷酮和N-甲基己内酰胺之类的溶剂,或这些溶剂的任何所需混合物。
为了进行根据本发明的方法,使起始组分A)和B)通常在40至180℃,优选50至150℃的温度下相互反应,其中遵循2∶1至400∶1,优选4∶1至140∶1的NCO/OH当量比,优选直至实现理论计算的NCO含量,其中可以例如通过NCO含量的滴定测定监测反应进程。优选通过根据DIN EN ISO 11909:2007-05的滴定手段测定NCO含量。
在此,多异氰酸酯组分A)与非离子亲水化合物B)的反应可以进行,例如直至对应于完全氨基甲酸酯化的NCO含量。这一反应可以无催化地进行,但是为了反应加速,也可以一同使用聚氨酯化学中已知的常规氨基甲酸酯化催化剂,例如叔胺,如三乙胺、吡啶、甲基吡啶、苄基二甲基胺、N,N-桥亚乙基哌嗪、N-甲基哌啶、五甲基二亚乙基三胺、N,N-二甲基环己基胺、N,N′-二甲基哌嗪或金属盐,如氯化铁(III)、氯化锌、辛酸锌、2-乙基己酸锌、乙酰丙酮锌、辛酸锡(II)、乙基己酸锡(II)、棕榈酸锡(II)、二月桂酸二丁基锡(IV)、2-乙基-1-己酸锆(IV)、新癸酸锆(IV)、环烷酸锆(IV)、乙酰丙酮锆(IV)、三(乙基乙酰乙酸)铝、2-乙基己酸铋(III)、辛酸铋(III)、新癸酸铋(III)和乙醇酸钼。
这些催化剂任选以基于所用起始组分A)和B)的总量计0.001重量%至2.0重量%,优选0.01重量%至0.2重量%的量使用。
但是,该反应也可以根据EP-B 0 959 087中描述的方法进行,以使主要通过NCO/OH反应形成的氨基甲酸酯基团至少部分,优选在至少60摩尔%的程度上进一步反应以提供脲基甲酸酯基团。在这种情况下,反应搭档在上述NCO/OH当量比下在40至180℃,优选50至150℃的温度下,通常在如引用的专利文献中陈述的适用于加速脲基甲酸酯化反应的催化剂,特别是锌化合物,例如正辛酸锌(II)、2-乙基-1-己酸锌(II)或硬脂酸锌(II)存在下反应。
这些脲基甲酸酯化催化剂任选以基于所用起始组分A)和B)的总量计0.001重量%至2.0重量%,优选0.01重量%至0.2重量%的量使用。
在组分A)和B)的催化反应中,所用催化剂通常在实现所需NCO含量后化学终止。为此适用的催化剂毒物包括例如无机酸如盐酸、亚磷酸或磷酸,酰基氯如乙酰氯、苯甲酰氯或间苯二甲酰氯,磺酸和磺酸酯如甲磺酸、对甲苯磺酸、三氟甲磺酸、全氟丁烷磺酸、对甲苯磺酸甲酯和对甲苯磺酸乙酯,磷酸单烷基酯和磷酸二烷基酯如磷酸单十三烷基酯、磷酸二丁酯和磷酸二辛酯,以及甲硅烷基化的酸如甲磺酸三甲基甲硅烷基酯、三氟甲磺酸三甲基甲硅烷基酯、磷酸三(三甲基甲硅烷基)酯和磷酸二乙酯三甲基甲硅烷基酯。
如果所述类型的含磷催化剂毒物用于终止根据本发明的方法中任选一同使用的催化剂,其磷含量不计入由组分A)和B)组成的亲水改性多异氰酸酯的总磷含量。根据本发明的亲水改性多异氰酸酯中的总磷含量在这种情况下由多异氰酸酯组分A)和亲水化合物B)的磷含量和任选在根据本发明的方法中为了稳定或中和碱性催化剂残留物而在转化之前和/或期间加入的酸性磷化合物的量计算确定。
当使用无磷聚醚醇或含有小于50ppm磷的聚醚醇时,根据本发明的方法可再现地提供含脲二酮结构和任选脲酮亚胺基团的亲水多异氰酸酯,其具有基于含脲二酮结构和任选脲酮亚胺基团的亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯含量。脲二酮裂解和脲酮亚胺裂解如果有发生,在如此小的程度上发生,以致没有观察到对单体含量的不良影响。通过根据本发明的方法可获得或已获得的非离子亲水改性多异氰酸酯同样是本发明的主题。
本发明的另一个优选的实施方案是非离子亲水改性多异氰酸酯,其包含0.8至25摩尔%,特别优选1至20摩尔%,非常特别优选1至15摩尔%的脲二酮结构,在每种情况下基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%,和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构,和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯以及最大20ppm的磷。
本发明的另一个优选的实施方案是非离子亲水改性多异氰酸酯,其包含基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计0.8至25摩尔%的脲二酮结构,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%,和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构,和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯以及3至19ppm,优选5至18ppm的磷。
本发明的另一个优选的实施方案是非离子亲水改性多异氰酸酯,其包含基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计0.8至25摩尔%的脲二酮结构,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%,和基于脲二酮结构计小于0.15摩尔%,优选小于0.10摩尔%的脲酮亚胺结构,和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯以及最大20ppm的磷,并且其中脲酮亚胺结构的含量特别优选低于检出限。
本发明的另一个优选的实施方案是聚醚改性的多异氰酸酯,其包含基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计0.8至25摩尔%的脲二酮结构,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%,和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构,和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯以及最大20ppm的磷,其通过至少一种基于PDI和/或HDI的多异氰酸酯组分A)与B)至少一种具有统计平均5至25个环氧乙烷单元的聚乙二醇单甲基醚醇的反应可获得或已获得。
根据本发明的亲水性含脲二酮结构和任选脲酮亚胺基团的多异氰酸酯是用于通过异氰酸酯加聚法生产聚氨酯塑料的有价值的原材料。
为此,该亲水改性多异氰酸酯优选以水乳液的形式使用,其在水性双组分体系的情况下可与分散在水中的多羟基化合物组合反应。基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯的极低含量在此实现对商业使用者安全的操作。
任选的,可以在乳化前向根据本发明的方法制成的亲水改性多异氰酸酯加入另外的具有脂族、脂环族、芳脂族和/或芳族键合的异氰酸酯基团的非亲水化多异氰酸酯,特别是上述类型的涂料多异氰酸酯。在这样的混合物中,根据本发明的工艺产物起到随后混入比例的非亲水多异氰酸酯的乳化剂的作用。
根据本发明的非离子亲水改性多异氰酸酯混合物特别优选在使用基于下述粘合剂或粘合剂组分的水性涂料组合物的涂料生产中用作具有对异氰酸酯基团呈反应性的基团,特别是醇式羟基的溶解或分散在水中的涂料粘合剂或涂料粘合剂组分的交联剂。在此可通过在加工涂料组合物之前借助任何方法的简单搅拌或甚至通过使用双组分喷枪将任选为乳化形式的交联剂与粘合剂或粘合剂组分合并。
涂料粘合剂或涂料粘合剂组分在这种情况下包括例如:溶解或分散在水中的含羟基的聚丙烯酸酯,尤其是分子量范围为1000至20000的那些,其是以有机多异氰酸酯作为交联剂的有价值的双组分粘合剂,或聚酯和醇酸树脂化学中已知类型的分散在水中的任选氨基甲酸酯改性的含羟基的聚酯树脂。根据本发明的多异氰酸酯混合物的合适的反应搭档原则上包括溶解或分散在水中的所有包含异氰酸酯反应性基团的粘合剂。这些还包括例如分散在水中的聚氨酯或聚脲,其由于氨基甲酸酯或脲基团中存在的活性氢原子而可用多异氰酸酯交联。
本发明的另一主题是涂料组合物,其含有至少一种根据本发明的亲水性含脲二酮结构的多异氰酸酯。
在根据本发明作为水性涂料粘合剂的交联剂组分的用途中,根据本发明的亲水多异氰酸酯通常以相当于0.5∶1至2∶1的NCO基团:对NCO基团呈反应性的基团,特别是醇式羟基的当量比的量使用。
根据本发明的亲水多异氰酸酯也可任选以次要量混入到非官能水性涂料粘合剂中,以实现非常特定的性质,例如作为用于促进附着力的添加剂。
当然,根据本发明的亲水多异氰酸酯也可以以用本身为聚氨酯化学中已知的封闭剂封闭的形式,与上述水性涂料粘合剂或涂料粘合剂组分组合用于水性单组分PUR烤漆体系。合适的封闭剂是例如丙二酸二乙酯、乙酰乙酸乙酯、丙酮肟、丁酮肟、ε-己内酰胺、3,5-二甲基吡唑、1,2,4-三唑、二甲基-1,2,4-三唑、咪唑或这些封闭剂的任何所需混合物。
使用根据本发明的亲水多异氰酸酯配制的水性涂料的可被考虑的基底包括任何所需基底,例如金属、木材、玻璃、石材、陶瓷材料、混凝土、硬质和软质塑料、纺织品、皮革和纸,其在涂覆前也可任选带有常规底漆。
用根据本发明的亲水多异氰酸酯配制并任选可与涂料行业中常规的辅助剂和添加剂物质,例如流平助剂、彩色颜料、填料、消光剂或乳化剂掺合的水性涂料组合物在室温干燥的情况下也已具有良好的涂料技术性质。
但是,当然,它们也可以在强制条件下在升高的温度下干燥或通过在最多260℃的温度下烘烤干燥。
本发明的另一主题是用任选在热作用下固化的根据本发明的涂料组合物涂覆的基底。
由于它们优异的水可乳化性(这使得能够均匀、特别细碎分布在水性涂料粘合剂中),使用根据本发明的亲水多异氰酸酯作为水性聚氨酯涂料的交联剂组分产生具有出色的光学性质,尤其是高表面光泽、流平性和高透明度的涂层。
除作为水性2K-PUR涂料的交联剂组分的优选用途外,根据本发明的亲水多异氰酸酯还非常适合作为水性分散胶粘剂、皮革和纺织品涂料或纺织品印花浆的交联剂、作为无可吸附有机结合卤素(AOX)的纸助剂或作为矿物建筑材料,例如混凝土或砂浆物料的添加剂。
被指定为对根据本发明的方法优选的特征对本发明的其它主题也优选。
以下实施例用于例示本发明,但无论如何不应被理解为对保护范围施加任何限制。
实施例
除非另行指明,所有百分比数据基于重量计。
根据DIN EN ISO 11909:2007-05滴定测定NCO含量。
所有粘度测量用来自Anton Paar Germany GmbH(DE)公司的Physica MCR 51流变仪根据DIN EN ISO 3219:1994—10在250s-1的剪切速率下记录。
根据DIN EN ISO 10283:2007-11通过使用内标的气相色谱法测量残留单体含量。
用来自Lange,DE公司的LICO 400分光光度计根据DIN EN ISO 6271-2:2005-03通过分光光度法测量铂-钴色值。
异氰酸酯A)中存在的脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的含量(摩尔%)由(在Bruker DPX-400仪器上记录的)质子解耦13C-NMR谱的积分计算,并在每种情况下基于存在的脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的总和计。多异氰酸酯A)中任选存在的脲酮亚胺结构的含量(摩尔%)同样由质子解耦13C-NMR谱的积分计算,并基于脲二酮结构。在CDCl3中溶解的HDI多异氰酸酯的情况下,各个结构元素具有以下化学位移(以ppm计):脲二酮:157.1;异氰脲酸酯:148.4;亚氨基噁二嗪二酮:147.8、144.3和135.3;脲基甲酸酯:155.7和153.8、缩二脲:155.5;氨基甲酸酯:156.3;噁二嗪三酮:147.8和143.9;脲酮亚胺:158.7和144.6。
在微波消解后根据DIN EN ISO 11885:2009-09通过电感耦合等离子体原子发射光谱法(ICP-OES)测定起始多异氰酸酯A)和非离子亲水有机化合物B)中的磷含量。
起始化合物
多异氰酸酯A)
起始多异氰酸酯A1)
通过基于EP-A 330 966的实施例11的HDI的催化三聚制成的多异氰酸酯,其中改变在于在40%的粗制混合物的NCO含量下通过加入磷酸二丁酯终止该反应。随后,通过在130℃的温度和0.2毫巴的压力下的薄膜蒸馏分离出未转化的HDI。
产物具有以下特征值和组成:
起始多异氰酸酯A2)
基于WO 2018/153801的对比例2a通过使用5-氮螺[4.5]癸烷鎓二氟化氢盐在2-乙基己醇中的20%溶液作为催化剂的HDI三聚制成的多异氰酸酯,在44.8%的粗制混合物的NCO含量下通过加入与催化剂量相当量的十二烷基苯磺酸在异丙醇中的70%溶液终止反应,和随后通过在130℃的温度和0.2毫巴的压力下的薄膜蒸馏分离出未转化的HDI。
产物具有以下特征值和组成:
起始多异氰酸酯A3)
根据US 2004/0106762的实施例4通过热二聚和随后六甲基二硅氮烷催化的HDI三聚制成的多异氰酸酯。
产物具有以下特征值和组成:
起始多异氰酸酯A4)
根据EP-A 330966的实施例11制成的多异氰酸酯,其中改变在于使用2-乙基己醇代替2-乙基-1,3-己二醇作为催化剂溶剂并在42.5%的粗制混合物的NCO含量下通过加入磷酸二丁酯终止该反应。随后,通过在130℃的温度和0.2毫巴的压力下的薄膜蒸馏分离出未转化的HDI。
产物具有以下特征值和组成:
非离子亲水有机化合物B)
B1)甲氧基聚乙二醇MPEG 350,
OH值:160mg KOH/g,当量重量:351g/mol
pH值:6.3
磷含量:<1ppm
B2)甲氧基聚乙二醇MPEG 350,
OH值:162mg KOH/g,当量重量:346g/mol
pH值:3.7
磷含量:120ppm
B3)甲氧基聚乙二醇MPEG 500,
OH值:112mg KOH/g,当量重量:501g/mol
pH值:4.9
磷含量:<1ppm
B4)甲氧基聚乙二醇MPEG 500,
OH值:111mg KOH/g,当量重量:505g/mol
pH值:3.9
磷含量:110ppm
实施例1(本发明)
在搅拌下,在干燥氮气下在100℃下最初装载870克(4.50当量)多异氰酸酯组分A1),在30分钟内加入130克(0.37当量)非离子亲水有机化合物B1)并在此温度下进一步搅拌直至该混合物的NCO含量在大约2小时后已下降到对应于完全氨基甲酸酯化的值。冷却至室温后存在具有以下特征值的无色、完全清澈的亲水改性多异氰酸酯:
实施例2(本发明)
重复实施例1,其中在开始添加非离子亲水有机化合物B1)之前,向多异氰酸酯组分A1)加入0.5克(基于总批量计50ppm)作为稳定剂的磷酸二丁酯。获得具有以下特征值的无色、完全清澈的亲水改性多异氰酸酯:
实施例3(对比)
根据实施例1中描述的方法,使870克(4.50当量)多异氰酸酯组分A1)与130克(0.38当量)非离子亲水有机化合物B2)反应。获得具有以下特征值的无色、完全清澈的亲水改性多异氰酸酯:
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实施例4(本发明)
在搅拌下,在干燥氮气下在100℃下最初装载830克(4.64当量)多异氰酸酯组分A2),在30分钟内加入170克(0.48当量)非离子亲水有机化合物B1)并在此温度下进一步搅拌直至该混合物的NCO含量在大约2小时后已下降到对应于完全氨基甲酸酯化的值。冷却至室温后存在具有以下特征值的轻微黄色、完全清澈的亲水改性多异氰酸酯:
实施例5(对比)
根据实施例3中描述的方法,使830克(4.64当量)多异氰酸酯组分A2)与170克(0.48当量)非离子亲水有机化合物B2)反应。获得具有以下特征值的轻微黄色、完全清澈的亲水改性多异氰酸酯:
实施例6(本发明)
在搅拌下,在干燥氮气下在80℃下最初装载800克(4.40当量)多异氰酸酯组分A3),在30分钟内加入200克(0.40当量)非离子亲水有机化合物B3)并在此温度下进一步搅拌直至该混合物的NCO含量在大约3.5小时后已下降到对应于完全氨基甲酸酯化的值。冷却至室温后存在具有以下特征值的轻微黄色、完全清澈的亲水改性多异氰酸酯:
实施例7(对比)
根据实施例5中描述的方法,使800克(4.13当量)多异氰酸酯组分A3)与200克(0.40当量)非离子亲水有机化合物B4)反应。获得具有以下特征值的无色、完全清澈的亲水改性多异氰酸酯:
实施例1、2、4和6证明,含有脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构的起始多异氰酸酯A1)、A2)和A3)与无磷聚醚醇在100℃下的反应提供单体含量小于0.10%的非离子亲水化多异氰酸酯。相比之下,对比例3、5和7表明,当各自的起始多异氰酸酯和聚醚醇中的磷量总计大于20ppm时,起始多异氰酸酯A1)、A2)和A3)与含有多于50ppm磷的聚醚醇的反应提供单体含量大于0.10%的亲水改性多异氰酸酯。
实施例8至13(本发明和对比)
根据实施例1中描述的方法,使多异氰酸酯组分A1)和A4)各自与由聚醚醇B1)和B2)的混合物组成并含有不同量的磷的非离子亲水有机化合物反应。下表显示反应混合物的各自组成、聚醚组分和多异氰酸酯组分的总磷含量和所得反应产物的特征值。
*包括来自磷酸二丁酯(稳定剂)的P
实施例8、10和12表明,含有脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构的起始多异氰酸酯A1)和A4)与磷含量最大50ppm的聚醚醇在100℃下的反应在它们的总磷含量最大20ppm时提供单体含量小于0.10%的非离子亲水化多异氰酸酯。
与此相比,由相同的多异氰酸酯组分与含有多于50ppm磷的聚醚醇混合物开始,对比例9、11和13在反应混合物中的总磷含量大于20ppm时提供单体含量在每种情况下大于0.10%的亲水改性多异氰酸酯。
Claims (15)
1.生产具有基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯含量的亲水改性多异氰酸酯的方法,其包括以下组分的反应
A)至少一种具有脂族、脂环族、芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分,其包含至少脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构,与
B)至少一种非离子亲水有机化合物,其包含至少一个异氰酸酯反应性基团,
其中所述非离子亲水有机化合物B)具有最大50ppm的磷含量,并且基于所述亲水改性多异氰酸酯的组分A)和B)计的总磷含量最大20ppm。
2.如权利要求1中所述的方法,其特征在于所述多异氰酸酯组分A)具有至少0.6摩尔%,优选0.8至25摩尔%的脲二酮结构的含量,在每种情况下基于多异氰酸酯中存在的所有脲二酮、任选异氰脲酸酯、亚氨基噁二嗪二酮、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量计,其中多异氰酸酯中存在的所有亚氨基噁二嗪二酮、脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、氨基甲酸酯和/或噁二嗪三酮结构的总量合计为100摩尔%。
3.如权利要求1和2任一项中所述的方法,其特征在于所述多异氰酸酯组分A)含有至少脲二酮和异氰脲酸酯结构。
4.如权利要求1和2任一项中所述的方法,其特征在于所述多异氰酸酯组分A)具有仅脂族和/或脂环族键合的异氰酸酯基团。
5.如权利要求1至4任一项中所述的方法,其特征在于所述多异氰酸酯组分A)是基于PDI、HDI、IPDI和/或2,4′-和4,4′-二环己基甲烷二异氰酸酯的那些。
6.如权利要求1至5任一项中所述的方法,其特征在于所述非离子亲水有机化合物B)是具有每分子统计平均5至50个环氧乙烷单元的一元或多元聚环氧烷聚醚醇。
7.如权利要求6中所述的方法,其特征在于所述非离子亲水有机化合物B)是纯聚环氧乙烷聚醚醇或混合聚环氧烷聚醚醇,其环氧烷单元在至少70摩尔%的程度上由环氧乙烷单元组成。
8.如权利要求6和7中所述的方法,其特征在于所述非离子亲水化合物B)具有4.0至8.0,优选4.5至7.5,特别优选5.0至7.0的作为5%水溶液测得的pH值。
9.如权利要求1至8任一项中所述的方法,其特征在于所述非离子亲水化合物B)以基于所用起始组分A)和B)的总量计最多30重量%,优选2重量%至25重量%,特别优选5至20重量%,非常特别优选9重量%至17重量%的量使用。
10.如权利要求1至9任一项中所述的方法,其特征在于所述非离子亲水有机化合物B)具有最大40ppm,优选最大30ppm的磷含量,特别优选不含可检出的磷,其中在微波消解后根据DIN EN ISO 11885:2009-09通过电感耦合等离子体原子发射光谱法(ICP-OES)测定磷含量。
11.如权利要求1至10任一项中所述的方法,其特征在于由组分A)和B)组成的亲水改性多异氰酸酯中的总磷含量为3至19ppm,特别优选5至18ppm。
12.非离子亲水改性多异氰酸酯,其包含脲二酮结构和基于脲二酮结构计小于0.20摩尔%的脲酮亚胺结构和基于亲水改性多异氰酸酯的固含量计小于0.10重量%的单体二异氰酸酯以及最大20ppm的磷。
13.如权利要求12中所述的非离子亲水改性多异氰酸酯作为聚氨酯塑料生产中的起始组分的用途。
14.涂料组合物,其含有如权利要求12中所述的非离子亲水改性多异氰酸酯。
15.用任选在热作用下固化的如权利要求14中所述的涂料组合物涂覆的基底。
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EP20214008.3 | 2020-12-15 | ||
EP20214008.3A EP4015546A1 (de) | 2020-12-15 | 2020-12-15 | Nichtionisch hydrophilierte polyisocyanate mit sehr niedrigem monomergehalt |
PCT/EP2021/085844 WO2022129140A1 (de) | 2020-12-15 | 2021-12-15 | Nichtionisch hydrophilierte polyisocyanate mit sehr niedrigem monomergehalt |
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US (1) | US20240010784A1 (zh) |
EP (2) | EP4015546A1 (zh) |
CN (1) | CN116568720A (zh) |
WO (1) | WO2022129140A1 (zh) |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1954093C3 (de) | 1968-11-15 | 1978-12-21 | Mobay Chemical Corp., Pittsburgh, Pa. (V.St.A.) | Verfahren zur Herstellung von polymeren organischen Isocyanaten |
DE2414413C3 (de) | 1974-03-26 | 1978-08-24 | Bayer Ag, 5090 Leverkusen | Verwendung von Lösungen von Polyisocyanaten mit Isocyanuratstruktur in Zweikomponenten-Polyurethan-Lacken |
DE2452532C3 (de) | 1974-11-06 | 1978-08-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Polyisocyanaten mit Isocyanurat-Struktur |
DE2641380C2 (de) | 1976-09-15 | 1989-11-23 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Polyisocyanaten mit Isocyanuratstruktur |
DE3700209A1 (de) | 1987-01-07 | 1988-07-21 | Bayer Ag | Verfahren zur herstellung von polyisocyanaten mit biuretstruktur |
DE3806276A1 (de) | 1988-02-27 | 1989-09-07 | Bayer Ag | Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung |
DE3811350A1 (de) | 1988-04-02 | 1989-10-19 | Bayer Ag | Verfahren zur herstellung von isocyanuratpolyisocyanaten, die nach diesem verfahren erhaltenen verbindungen und ihre verwendung |
DE3814167A1 (de) | 1988-04-27 | 1989-11-09 | Bayer Ag | Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung |
DE3900053A1 (de) | 1989-01-03 | 1990-07-12 | Bayer Ag | Verfahren zur herstellung von uretdion- und isocyanuratgruppen aufweisenden polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und ihre verwendung in zweikomponenten-polyurethanlacken |
DE3928503A1 (de) | 1989-08-29 | 1991-03-07 | Bayer Ag | Verfahren zur herstellung von loesungen von isocyanuratgruppen aufweisenden polyisocyanaten in lackloesungsmitteln und ihre verwendung |
DE4136618A1 (de) * | 1991-11-07 | 1993-05-13 | Bayer Ag | Wasserdispergierbare polyisocyanatgemische |
DE19611849A1 (de) | 1996-03-26 | 1997-10-02 | Bayer Ag | Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung |
DE19654429A1 (de) * | 1996-12-24 | 1998-06-25 | Bayer Ag | Wasserdispergierbare Polyisocyanatgemische als Additive für Beton |
DE69828290T2 (de) | 1997-08-12 | 2005-12-08 | Rhodia Chimie | Verfahren zur Herstellung einer Polyisocyanatzusammensetzung mit verringerter Viskosität |
ES2209274T3 (es) | 1998-05-22 | 2004-06-16 | Bayer Aktiengesellschaft | Mezclas de poliisocianatos modificadas mediante polieteres dispersables. |
DE59902995D1 (de) | 1998-06-02 | 2002-11-14 | Bayer Ag | Verfahren zur Herstellung Iminooxadiazindiongruppen enhaltender Polyisocyanate |
US6562076B2 (en) | 1998-08-31 | 2003-05-13 | Xerox Corporation | Extending application behavior through active properties attached to a document in a document management system |
CN103987750B (zh) | 2011-11-29 | 2017-06-06 | 科思创德国股份有限公司 | 制备多异氰酸酯的方法及其应用 |
HUE035077T2 (en) | 2013-12-10 | 2018-05-02 | Covestro Deutschland Ag | Polyisocyanates containing Iminoadadiazindion groups |
ES2681659T3 (es) | 2014-02-18 | 2018-09-14 | Covestro Deutschland Ag | Procedimiento para la modificación de isocianatos mediante el uso de catalizadores con secuencia de N-P-N |
US9850338B2 (en) | 2014-02-18 | 2017-12-26 | Covestro Deutschland Ag | Process for isocyanate modification using spirocyclic ammonium salts as catalyst |
JP6892825B2 (ja) * | 2015-03-17 | 2021-06-23 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | 1,5−ジイソシアナトペンタンを基礎とするシラン基含有のポリイソシアネート |
KR20180041665A (ko) | 2015-08-17 | 2018-04-24 | 코베스트로 도이칠란트 아게 | 촉매로서 시클릭 암모늄 염을 사용하는 이소시아네이트의 개질 방법 |
CN108699204B (zh) | 2016-03-09 | 2020-10-16 | 旭化成株式会社 | 多异氰酸酯组合物、涂覆组合物、水系涂覆组合物和涂覆基材 |
US20200002462A1 (en) | 2017-02-22 | 2020-01-02 | Covestro Deutschland Ag | Method for modifying at least pentamethylene diisocyanate by means of spirocyclic ammonium salts as catalyst |
EP3543270A1 (de) * | 2018-03-23 | 2019-09-25 | Covestro Deutschland AG | Katalysatorsystem für uretdiondispersionen |
-
2020
- 2020-12-15 EP EP20214008.3A patent/EP4015546A1/de not_active Ceased
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2021
- 2021-12-15 WO PCT/EP2021/085844 patent/WO2022129140A1/de active Application Filing
- 2021-12-15 CN CN202180084200.8A patent/CN116568720A/zh active Pending
- 2021-12-15 US US18/267,164 patent/US20240010784A1/en active Pending
- 2021-12-15 EP EP21836173.1A patent/EP4263649A1/de active Pending
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EP4263649A1 (de) | 2023-10-25 |
US20240010784A1 (en) | 2024-01-11 |
WO2022129140A1 (de) | 2022-06-23 |
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