EP4263649A1 - Non-ionic hydrophilized polyisocyanates having a very low monomer content - Google Patents
Non-ionic hydrophilized polyisocyanates having a very low monomer contentInfo
- Publication number
- EP4263649A1 EP4263649A1 EP21836173.1A EP21836173A EP4263649A1 EP 4263649 A1 EP4263649 A1 EP 4263649A1 EP 21836173 A EP21836173 A EP 21836173A EP 4263649 A1 EP4263649 A1 EP 4263649A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- structures
- uretdione
- ppm
- mol
- polyisocyanates
- 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 153
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 153
- 239000000178 monomer Substances 0.000 title description 13
- 238000000034 method Methods 0.000 claims abstract description 52
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 70
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 51
- 229910052698 phosphorus Inorganic materials 0.000 claims description 51
- 239000011574 phosphorus Substances 0.000 claims description 51
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 26
- 229920000570 polyether Polymers 0.000 claims description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 150000002894 organic compounds Chemical class 0.000 claims description 23
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 21
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical compound N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 20
- 150000001298 alcohols Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 9
- 150000002433 hydrophilic molecules Chemical class 0.000 claims description 8
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 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
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 28
- 239000011230 binding agent Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000003776 cleavage reaction Methods 0.000 description 9
- 230000007017 scission Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- -1 hydrocarbon radicals Chemical class 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229920002396 Polyurea Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical class CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class 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
- 239000004971 Cross linker Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 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
- 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
- 238000004817 gas chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 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
- 239000010985 leather Substances 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-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
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-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
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 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
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-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
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-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
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-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
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-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
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- DEVWEFBXXYMHIL-UHFFFAOYSA-N CCCOP(O)=O Chemical compound CCCOP(O)=O DEVWEFBXXYMHIL-UHFFFAOYSA-N 0.000 description 1
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 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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- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- QPKOILOWXGLVJS-UHFFFAOYSA-N bis(2-methylpropoxy)-oxophosphanium Chemical compound CC(C)CO[P+](=O)OCC(C)C QPKOILOWXGLVJS-UHFFFAOYSA-N 0.000 description 1
- FNYKAWJEEWSNEH-UHFFFAOYSA-K bismuth;3,3,5,5-tetramethylhexanoate Chemical compound [Bi+3].CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O FNYKAWJEEWSNEH-UHFFFAOYSA-K 0.000 description 1
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- HDFFVHSMHLDSLO-UHFFFAOYSA-M dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)([O-])OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-M 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical class CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BJLZAAWLLPMZQR-UHFFFAOYSA-N oxo-di(propan-2-yloxy)phosphanium Chemical compound CC(C)O[P+](=O)OC(C)C BJLZAAWLLPMZQR-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical class 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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Chemical group 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003459 sulfonic acid esters 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
- 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-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
- NTJPIRDYMVYFNP-UHFFFAOYSA-M trimethylsilylmethanesulfonate Chemical compound C[Si](C)(C)CS([O-])(=O)=O NTJPIRDYMVYFNP-UHFFFAOYSA-M 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 Chemical group 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
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
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- 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
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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- 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
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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- 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
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- 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
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C08G2150/00—Compositions for coatings
Definitions
- the invention relates to a process for the production of hydrophilically modified polyisocyanates with a low content of monomeric diisocyanates, the polyisocyanates obtainable or obtained by this process and the use of these for the production of polyurethane plastics.
- the invention also relates to coating compositions containing the nonionically hydrophilically modified polyisocyanates and to the substrates coated with these coating compositions.
- Aqueous paint systems have become firmly established for various areas of application as an environmentally friendly alternative to solvent-based coating materials.
- Hydrophilic-modified polyisocyanates play a special role as raw materials for high-quality water-based paints, since as water-dispersible crosslinking components they enable the formulation of water-based two-component polyurethane (2K-PUR) paints.
- a simple and inexpensive method for preparing water-dispersible polyisocyanates is the proportionate reaction of hydrophobic polyisocyanates with hydrophilic polyether alcohols (see, for example, EP-A 0 959 087, page 2, lines 25-46). On an industrial scale, this reaction is usually carried out at temperatures of from about 80 to 130° C. in order to ensure reaction times that are economically acceptable.
- hydrophilic polyisocyanates will also come under the restriction imposed by the European Chemicals Agency (ECHA) on handling substances or mixtures with a content of free monomeric diisocyanates of 0.10% by weight or more. Hydrophilic polyisocyanates with less than 0.10% of monomeric diisocyanates are therefore desirable for reliable commercial use as crosslinking components in water-based 2K PUR coatings.
- ECHA European Chemicals Agency
- EP 3 543 270 A1 relates to a catalyst system for uretdione dispersions, in which no hydrophilic polyisocyanates are described which have a residual monomer content of less than 0.10% by weight, based on the solids content.
- US Pat. No. 5,252,696 A and EP 0 850 896 A1 describe water-dispersible polyisocyanates without going into detail, for example, about the residual monomer content.
- WO2016/146474 A1 discloses polyisocyanates containing silane groups which are present in organic solvents.
- EP 3 428 207 A1 describes hydrophilic polyisocyanate compositions with specific ratios of uretonimine and iminooxadiazinedione groups, based in each case on the isocyanurate groups present, resulting in a ratio of uretonimine to uretdione groups of 0.20 to 50 mol %.
- the uretonimine groups are intentionally formed by heating the polyisocyanates prior to the hydrophilization reaction.
- the disadvantage of this is that the thermal labile uretonimine groups must be present and there is no guarantee that the content of monomeric diisocyanates can be reliably kept below 0.10% by weight.
- the object of the present invention was therefore to provide a new process for preparing nonionically hydrophilically modified polyisocyanates, according to which uretdione structures and optionally hydrophobic polyisocyanates containing uretonimine groups can also be reacted with hydrophilic polyether alcohols without a noticeable increase due to uretdione cleavage and uretonimine cleavage of monomeric diisocyanates above 0.10% by weight.
- the process according to the invention is based on the surprising observation that the tendency towards uretdione cleavage and uretonimine cleavage and thus the increase in the content of monomeric diisocyanates correlates to a high degree with the quality of the polyether alcohols used.
- the polyether alcohols used for hydrophilizing polyisocyanates are usually prepared by alkali-catalyzed addition of alkylene oxides, in particular ethylene oxide, onto starter molecules having at least one active hydrogen atom. Following the addition reaction, the alkaline catalyst is then generally neutralized with an inorganic or organic acid and the salt that forms is removed from the polyether alcohol.
- the present invention relates to a process for the preparation of hydrophilically modified polyisocyanates containing less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, comprising a reaction of
- nonionic hydrophilic organic compound B) at least one nonionic hydrophilic organic compound which has at least one isocyanate-reactive group, the nonionic hydrophilic organic compound B) having a phosphorus content of at most 50 ppm, and the total phosphorus content based on components A) and B) of the hydrophilically modified polyisocyanate is at most 20 ppm.
- the invention also relates to nonionically hydrophilically modified polyisocyanates containing uretdione structures and less than 0.20 mol % of uretonimine structures, based on the uretdione structures, and less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates , and have a maximum of 20 ppm of phosphorus, and their use as starting components in the production of polyurethane plastics, in particular as crosslinkers for water-soluble or water-dispersible binders or binder components with isocyanate-reactive groups in the production of coatings using aqueous coating compositions based on such binders or binder components.
- the expressions “comprising” or “containing” preferably mean “consisting essentially of” and particularly preferably “consisting of”.
- An "organic compound” or “organic radical” contains at least one moiety that comprises a covalent carbon-hydrogen bond.
- aliphatic is defined as non-aromatic hydrocarbon groups that are saturated or unsaturated.
- aromatic is defined as hydrocarbon radicals consisting of both an aromatic and a saturated or unsaturated hydrocarbon group bonded directly to the aromatic radical.
- alicyclic or “cycloaliphatic” is defined as an optionally substituted carbocyclic or heterocyclic compound or moiety that is not aromatic.
- hydrophilic is defined as a water solubility of a compound of at least 500 g/litre, preferably complete water solubility, and the term “hydrophobic” as a water solubility of a compound of at most 100 g/litre, preferably complete insolubility in water, each determined at 20°C.
- At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compounds described herein, this specification does not refer to the absolute amount of molecules, but to the type of component. "At least one non-ionic hydrophilic organic compound” therefore means, for example, that only one type of compound or several different types of compounds of this type can be present, without providing information about the amount of the individual compounds.
- Suitable polyisocyanates A) for the process according to the invention are any polyisocyanates which have been prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates and have at least uretdione structures.
- Suitable diisocyanates for preparing the polyisocyanates A) can be used in various ways, for example by phosgenation of the corresponding diamines in the liquid or gas phase or in a phosgene-free way, such as. B. by thermal urethane cleavage.
- Preferred diisocyanates are those in the molecular weight range from 140 to 400 with aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanate groups, such as, for example, B.
- 1,4-diisocyanatobutane 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2, 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl )-cyclohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane, 1-isocyanato-l-methyl-4(3)
- TMXDI tetramethylxylylene diisocyanate
- TDI 2,4- and 2,6-diisocyanatotoluene
- MDI 2,4'- and 4,4'-diisocyanatodiphenylmethane
- the polyisocyanates A) used in the process according to the invention may also optionally have isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures.
- the polyisocyanates A) are prepared by methods known per se, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, in 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 and DE-A 3 928 503 or in 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 and EP-A 3,337,836 are described by way of example.
- the actual modification reaction is generally followed by a further process step for separating off the unreacted excess monomeric diisocyanates.
- This removal of monomers is carried out by methods known per se, preferably by thin-layer distillation in vacuo or by extraction with suitable solvents which are inert towards isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
- polyisocyanates A which have a monomeric diisocyanate content of less than 0.14% by weight, preferably less than 0.12% by weight, particularly preferably less than 0.10% by weight. % exhibit.
- the residual monomer content is determined according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard.
- the polyisocyanate component A) used in the process according to the invention can optionally contain phosphorus in an amount of up to 28 ppm, preferably up to 25 ppm, particularly preferably up to 20 ppm, which is present, for example, in the form of blocked oligomerization catalysts.
- these phosphorus contents are determined by inductively coupled plasma atomic emission spectrometry (ICP-OES) in accordance with DIN EN ISO 11885:2009-09 after microwave digestion.
- the detection limit for phosphorus with this method is ⁇ 1 ppm.
- the content of uretdione structures is preferably at least 0.6 mol %, more preferably from 0.8 to 25 mol %, particularly preferably from 1 to 20 mol %, very particularly preferably from 1 up to 15 mol %, in each case based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate, the total amount of all iminooxadiazinedione, uretdione, Isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures yields 100 mol%.
- the content of uretonimine structures in the polyisocyanates A), if detectable at all, is less than 0.20 mol %, preferably less than 0.15 mol %, particularly preferably less than 0.10 mol %, based on the uretdione structures.
- the contents (mol %) of the uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanates A) are calculated from the integrals of proton-decoupled 13 C-NMR spectra and relate based on the total of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures.
- any uretonime structures present in the polyisocyanates A) were also calculated from the integrals of the proton-decoupled 13 C-NMR spectra and relate to uretdione structures.
- the individual structural elements have the following chemical shifts (in ppm): uretdione: 157.1; Isocyanurate: 148.4; iminooxadiazinedione: 147.8, 144.3 and 135.3; allophanate: 155.7 and 153.8, biuret: 155.5; urethane: 156.3; oxadiazinetrione: 147.8 and 143.9; Uretonimine: 158.7 and 144.6.
- Suitable polyisocyanates A) are also any mixtures of at least two polyisocyanates of the type mentioned, in which case polyisocyanates which are completely free of uretdione structures can also be used in these mixtures, provided the mixtures have the information given above for the polyisocyanates A) with regard to the contents correspond to uretdione and uretonimine structures.
- Preferred polyisocyanates A) are those of the type mentioned which, in addition to uretdione structures, also contain at least isocyanurate structures.
- Polyisocyanates with araliphatically and/or aromatically bound isocyanate groups are used in the process according to the invention, if at all, preferably in amounts of at most 20% by weight, particularly preferably at most 10% by weight, based on the total amount of polyisocyanates A).
- Particularly preferred polyisocyanates A) for the process according to the invention are those of the type mentioned with exclusively aliphatically and/or cycloaliphatically bound isocyanate groups which are free of uretonimine groups or in which uretonimine groups are not detectable.
- Very particularly preferred polyisocyanates A) are those based on PDI, HDI, IPDI and/or 2,4'- and 4,4'-diisocyanatodicyclohexylmethane.
- the polyisocyanates A) mentioned above as being suitable, preferred, particularly preferred and very particularly preferred contain uretdione structures and, if appropriate, preferably isocyanurate structures, and have an average NCO functionality of from 2.3 to 5.0, preferably from 2.5 to 4.5, and an isocyanate group content of from 6.0 to 26.0% by weight, preferably from 8.0 to 25.0% by weight, particularly preferably from 10.0 to 24.0% by weight.
- Starting compounds B) for the process according to the invention are any nonionic hydrophilic organic compounds which have at least one isocyanate-reactive group and which have a phosphorus content of at most 50 ppm.
- the silane compounds which are reactive toward isocyanate groups and are explicitly mentioned in WO 2016/146474 A1 are preferably excluded from the starting compounds B) of the present invention.
- Suitable starting compounds B) are, for example, monohydric or polyhydric polyalkylene oxide polyether alcohols having a statistical average of 5 to 50 ethylene oxide units per molecule, as are accessible in a manner known per se by alkoxylating suitable starter molecules (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, Verlag Chemie, Weinheim, p. 31-38).
- suitable starter molecules can be, for example, any mono- or polyhydric alcohols in the molecular weight range from 32 to 300, such as. B.
- Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any order or as a mixture in the alkoxylation reaction.
- Suitable polyether alcohols are either pure polyethylene oxide polyether alcohols or mixed polyalkylene oxide polyethers, the alkylene oxide units of which consist of at least 70 mol %, preferably at least 80 mol %, of ethylene oxide units.
- Preferred polyalkylene oxide polyether alcohols B) are those which have been prepared using the abovementioned monoalcohols with a molecular weight in the range from 32 to 150 as starter molecules. More preferably, the nonionic hydrophilic organic compound B) is a monohydric or polyhydric polyalkylene oxide polyether alcohol having a statistical average of 5 to 50 ethylene oxide units, particularly preferably 5 to 25 ethylene oxide units, per molecule. Particularly preferred polyether alcohols are pure polyethylene glycol monomethyl ether alcohols which have a statistical average of 5 to 50, very particularly preferably 5 to 25, ethylene oxide units.
- the nonionic hydrophilic compounds B) preferably have a pH, measured on a 5% solution in water, of 4.0 to 8.0, preferably 4.5 to 7.5, particularly preferably 5.0 to 7 ,0 on.
- nonionic hydrophilic compounds B) can be freely selected over a wide range in the process according to the invention.
- nonionic hydrophilic compounds B) are preferably used in amounts of up to 30% by weight, particularly preferably from 2 to 25% by weight, very particularly preferably from 5 to 20% by weight and in particular from 9 to 17% by weight %, based on the total amount of starting components A) and B) used.
- the nonionic hydrophilic compounds B) have a phosphorus content of at most 50 ppm, preferably at most 40 ppm, particularly preferably at most 30 ppm and very particularly preferably no detectable phosphorus, the phosphorus contents being determined by inductively coupled plasma atomic Emission spectrometry (ICP-OES) according to DIN EN ISO 11885:2009-09 after microwave digestion.
- ICP-OES inductively coupled plasma atomic Emission spectrometry
- the total phosphorus content in the hydrophilically modified polyisocyanates according to the invention consisting of components A) and B), which can also be determined by the ICP-OES method described above, is at most 20 ppm, preferably from 3 to 19 ppm, particularly preferably from 5 to 18ppm.
- the total phosphorus content in the hydrophilically modified polyisocyanates according to the invention can also be determined by calculation in a simple manner from the phosphorus contents of the polyisocyanate components A) and the hydrophilic compounds B).
- the calculation of the total phosphorus content also includes the amounts of phosphorus which, in the process according to the invention, may be present in the form of acidic phosphorus compounds of the polyisocyanate component A) and/or the nonionic hydrophilic organic compound B) before and/or during the reaction for stabilization or Neutralization of basic catalyst residues are added.
- Such acidic phosphorus compounds are, for example, phosphoric acid, phosphoric acid esters, such as.
- Suitable solvents which are inert towards the reactive groups of the starting components, in particular towards isocyanate groups, can also be used.
- suitable solvents are, for example, the conventional paint solvents known per se, such as e.g.
- the starting components A) and B) are generally mixed at temperatures of from 40 to 180° C., preferably from 50 to 150° C., while maintaining an NCO/OH equivalent ratio of from 2:1 to 400:1, preferably from 4: 1 to 140: 1, preferably until the theoretically calculated NCO content is reached, the course of the reaction being monitored by z.
- B. titrimetric determination of the NCO content can be followed.
- the NCO content is preferably determined titrimetrically according to DIN EN ISO 11909:2007-05.
- the reaction of the polyisocyanate component A) with the nonionic hydrophilic compounds B) can be carried out, for example, up to the NCO content corresponding to complete urethanization.
- This reaction can take place without catalysis, but the usual urethanization catalysts known from polyurethane chemistry can also be used to accelerate the reaction, for example tert.
- amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N'-dimethylpiperazine or metal salts such as iron(III) chloride, zinc chloride, zinc octoate, Zinc 2-ethylcaproate, Zinc acetylacetonate, Tin(II) octoate, Tin(II) ethylcaproate, Tin(II) palmitate, Dibutyltin(IV) dilaurate, Zirconium(IV)-2-ethyl-l- hexanoate, zirconium(IV) neodecanoate, zirconium(IV) naphthenate, zirconium(IV) acetylacetonate, aluminum tri(ethylaceto
- catalysts are used in amounts of 0.001 to 2.0% by weight, preferably 0.01 to 0.2% by weight, based on the total amount of starting components A) and B) used.
- the reaction can, for example, also be carried out according to the process described in EP-B 0 959 087 in such a way that the urethane groups primarily formed by the NCO/OH reaction are at least partially, preferably at least 60 mol %, further converted to allophanate groups.
- reactants are reacted in the abovementioned NCO/OH equivalent ratio at temperatures of 40 to 180° C., preferably 50 to 150° C., generally in the presence of the catalysts, in particular zinc compounds, which are suitable for accelerating the allophanatization reaction and are listed in the cited patent , such as B.
- allophanatization catalysts are used in amounts of 0.001 to 2.0% by weight, preferably 0.01 to 0.2% by weight, based on the total amount of starting components A) and B) used.
- Catalyst poisons suitable for this purpose are, for example, inorganic acids such as hydrochloric acid, phosphorous acid or phosphoric acid, acid chlorides such as acetyl chloride, benzoyl chloride or isophthaloyl dichloride, sulfonic acids and sulfonic acid esters such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, methyl p-toluenesulfonate and -ethyl ester, mono- and dialkyl phosphates such as Monotridecyl phosphate, dibutyl phosphate and dioctyl phosphate, but also silylated acids, such as trimethylsilyl methanesulfonate,
- phosphorus-containing catalyst poisons of the type mentioned are used to stop the catalysts that may be used in the process according to the invention, their phosphorus content is not included in the total phosphorus content of the hydrophilically modified polyisocyanate consisting of components A) and B).
- the total content of phosphorus in the hydrophilically modified polyisocyanates according to the invention is determined by calculation from the phosphorus contents of the polyisocyanate components A) and the hydrophilic compounds B) and, if appropriate, in the process according to the invention before and/or during the reaction for the stabilization or neutralization of basic catalyst residues added amounts acidic phosphorus compounds.
- the process according to the invention gives reproducible uretdione structures and optionally hydrophilic polyisocyanates containing uretonimine groups with a content of monomeric diisocyanates of less than 0.10% by weight, based on the solids content of hydrophilically modified polyisocyanates containing uretdione structures and optionally uretonimine groups. Cleavage of uretdione and uretonimine occurs, if at all, to such a small extent that no negative influence on the monomer content can be observed.
- the present invention also relates to the nonionically hydrophilically modified polyisocyanates obtainable or obtained by the process according to the invention.
- a further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol %, particularly preferably from 1 to 20 mol % and very particularly preferably from 1 to 15 mol % of uretdione structures, based in each case on the total amount all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate, the total amount of all im Polyisocyanate present iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and / or oxadiazinetrione structures results in 100 mol%, and contain less than 0.20 mol% of uretonimine structures based on the uretdione structures and less than 0, 10% by weight of monomeric diisocyanates, based on
- a further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol % uretdione structures, based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mole %, and less than 0.20 mole % based on uretonimine structures on the uretdione structures and contain less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and from 3 to 19 ppm, preferably from 5 to 18 pp
- a further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol % uretdione structures, based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mole %, and less than 0.15 mole %, preferably less than 0.10 mol % of uretonimine structures based on the uretdione structures and less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and at most 20 ppm
- polyether-modified polyisocyanates the 0.8 to 25 mol% uretdione, based on the total amount of all present in the polyisocyanate uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and /or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mol%, and less than 0.20 mol% of uretonimine structures based on which contain uretdione structures and have less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and at most 20 ppm of phosphorus, obtainable or obtained by
- hydrophilic polyisocyanates according to the invention containing uretdione structures and optionally uretonimine groups are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process.
- the hydrophilically modified polyisocyanates are preferably used in the form of aqueous emulsions which can be reacted in combination with water-dispersed polyhydroxyl compounds in the sense of aqueous two-component systems.
- the very low content of monomeric diisocyanates of less than 0.10% by weight, based on the solids content of the hydrophilically modified polyisocyanates, enables safe handling for commercial users.
- non-hydrophilic polyisocyanates having aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups in particular paint polyisocyanates of the type mentioned above, can be added to the hydrophilically modified polyisocyanates prepared by the process according to the invention before emulsification.
- the products of the process according to the invention assume the function of an emulsifier for the proportion of non-hydrophilic polyisocyanates which is added subsequently.
- the nonionically hydrophilically modified polyisocyanate mixtures according to the invention are particularly preferably used as crosslinking agents for paint binders or paint binder components dissolved or dispersed in water with isocyanate-reactive groups, in particular alcoholic hydroxyl groups, in the production of coatings using aqueous coating compositions based on such binders or binder components .
- the crosslinking agent optionally in emulsified form, can be combined with the binders or binder components by simple stirring before the coating compositions are processed, using any desired method, or using two-component spray guns.
- paint binders or paint binder components examples are: polyacrylates containing hydroxyl groups, dissolved or dispersed in water, in particular those with a molecular weight in the range from 1,000 to 20,000, which, with organic polyisocyanates as crosslinkers, represent valuable two-component binders, or dispersed in water, optionally urethane-modified, Polyester resins containing hydroxyl groups of the type known from polyester and alkyd resin chemistry.
- Suitable reactants for the polyisocyanate mixtures according to the invention are in principle all binders which are dissolved or dispersed in water and contain isocyanate-reactive groups. This also includes, for example polyurethanes or polyureas dispersed in water which can be crosslinked with polyisocyanates because of the active hydrogen atoms present in the urethane or urea groups.
- Another subject of the present invention is a coating composition containing at least one polyisocyanate according to the invention containing hydrophilic uretdione structures.
- the hydrophilic polyisocyanates according to the invention are generally used in amounts corresponding to an equivalent ratio of NCO groups to NCO-reactive groups, in particular alcoholic hydroxyl groups, of 0.5:1 to 2:1 correspond to.
- hydrophilic polyisocyanates according to the invention can also be admixed in minor amounts to non-functional aqueous paint binders in order to achieve very specific properties, for example as an additive to improve adhesion.
- hydrophilic polyisocyanates according to the invention can also be used in a form blocked with blocking agents known per se from polyurethane chemistry in combination with the abovementioned aqueous paint binders or paint binder components in the sense of aqueous one-component PUR stoving systems.
- blocking agents are diethyl malonate, acetoacetic ester, acetone oxime, butanone oxime, s-caprolactam, 3,5-dimethylpyrazole, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole or any mixture of these blocking agents.
- any desired substrates can be used as substrates for the aqueous coatings formulated with the aid of the hydrophilic polyisocyanates according to the invention, such as, for example, B. metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textiles, leather and paper, which can optionally also be provided with conventional primers before coating.
- aqueous coating compositions formulated with the hydrophilic polyisocyanates according to the invention and to which the auxiliaries and additives customary in the coatings sector, such as e.g. B. leveling agents, color pigments, fillers, matting agents or emulsifiers can be incorporated, good paint properties even at room temperature drying.
- a further subject matter of the present invention is a substrate coated with a coating composition according to the invention, optionally cured under the action of heat.
- the use of the inventive leads hydrophilic polyisocyanates as a crosslinking component for aqueous polyurethane coatings to give coatings with excellent optical properties, in particular high surface gloss, leveling and high transparency.
- hydrophilic polyisocyanates according to the invention are outstandingly suitable as crosslinking agents for aqueous dispersion adhesives, leather and textile coatings or textile printing pastes, as paper auxiliaries that are free from adsorbable organically bound halogens (AOX), or else as an additive for mineral building materials, for example concrete or mortar masses.
- AOX organically bound halogens
- the NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.
- the residual monomer content was measured according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard.
- the platinum-cobalt color number was measured spectrophotometrically in accordance with DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, DE.
- the contents (mol %) of the uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanates A) were determined from the integrals of proton-decoupled 13 C-NMR spectra (recorded on a Bruker DPX-400 device) and relate in each case to the sum of the uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures present.
- any uretonime structures present in the polyisocyanates A) were also calculated from the integrals of the proton-decoupled 13 C-NMR spectra and relate to uretdione structures.
- the individual structural elements have the following chemical shifts (in ppm): uretdione: 157.1; Isocyanurate: 148.4; iminooxadiazinedione: 147.8, 144.3 and 135.3; allophanate: 155.7 and 153.8, biuret: 155.5; urethane: 156.3; oxadiazinetrione: 147.8 and 143.9; Uretonimine: 158.7 and 144.6.
- the phosphorus contents in the starting polyisocyanates A) and nonionic hydrophilic organic compounds B) were determined by inductively coupled plasma atomic emission spectrometry (ICP-OES) to DIN EN ISO 11885:2009-09 after microwave digestion.
- the detection limit for this method is ⁇ 1 ppm.
- Polyisocyanate prepared based on Comparative Example 2a of WO 2018/153801, by trimerization of HDI using a 20% solution of 5-azoniaspiro[4.5]decanium hydrogen difluoride in 2-ethylhexanol as a catalyst, stopping the reaction at an NCO content of Crude mixture of 44.8% by adding an amount of a 70% solution of dodecylbenzenesulfonic acid in isopropanol equivalent to the amount of catalyst and subsequent removal of the unreacted HDI by thin-layer distillation at a temperature of 130° C. and a pressure of 0.2 mbar.
- NCO content 23.1% monomeric HDI: 0.10%
- NCO content 17.2% monomeric HDI: 0.05% Viscosity (23°C): 3410 mPas
- Example 1 was repeated, with 0.5 g (50 ppm based on the total batch) of dibutyl phosphate being added as a stabilizer to the polyisocyanate component A1) before the start of the addition of the nonionic hydrophilic organic compound B1).
- a colorless, completely clear, hydrophilically modified polyisocyanate with the following characteristics was obtained:
- Examples 1, 2, 4 and 6 demonstrate that the reaction of the starting polyisocyanates A1), A2) and A3) containing uretdione structures and less than 0.20 mol % of uretonimine structures based on the uretdione structures with phosphorus-free polyether alcohols at 100° C provides nonionically hydrophilized polyisocyanates which have a monomer content of less than 0.10%.
- Comparative Examples 3, 5 and 7 show that the reaction of the same starting polyisocyanates A1), A2) and A3) with polyether alcohols containing more than 50 ppm phosphorus leads to hydrophilically modified polyisocyanates with monomer contents of more than 0.10%, if simultaneously the sum of phosphorus in the respective starting polyisocyanate and polyether alcohol is more than 20 ppm.
- the polyisocyanate components A1) and A4) were each reacted with nonionic hydrophilic organic compounds consisting of mixtures of the polyether alcohols B1) and B2) and containing different amounts of phosphorus.
- the table below shows the respective compositions of the reaction mixtures, the total phosphorus content of the polyether and polyisocyanate components and the characteristics of the reaction products obtained.
- Examples 8, 10 and 12 according to the invention show that the reaction of the starting polyisocyanates A1) and A4) containing uretdione structures and less than 0.20 mol % of uretonimine structures, based on the uretdione structures, with polyether alcohols whose phosphorus content is at most 50 ppm 100 °C nonionically hydrophilized polyisocyanates with monomer contents of less than 0.10% if their total phosphorus content is not more than 20 ppm.
- Comparative Examples 9, 11 and 13 starting from the same polyisocyanate components in combination with polyether alcohol mixtures which contained more than 50 ppm phosphorus, gave hydrophilically modified polyisocyanates with total phosphorus contents in the reaction mixture of more than 20 ppm and monomer contents of more than 0.10% in each case. .
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Abstract
The invention relates to a process for producing hydrophilically modified polyisocyanates having a very low content in monomeric diisocyanates, the polyisocyanates obtainable or obtained according to the process and the use thereof for producing polyurethane plastics. The invention further relates to coating agents that contain the non-ionic hydrophilically modified polyisocyanates and to the substrates coated with said coating agents.
Description
Nichtionisch hydrophilierte Polyisocyanate mit sehr niedrigem Monomergehalt Nonionically hydrophilized polyisocyanates with a very low monomer content
Die Erfindung betrifft ein Verfahren zur Herstellung hydrophil modifizierter Polyisocyanate mit niedrigem Gehalt an monomeren Diisocyanaten, die nach diesem Verfahren erhältlichen oder erhaltenen Polyisocyanate und die Verwendung dieser zur Herstellung von Polyurethankunststoffen. Außerdem betrifft die Erfindung Beschichtungsmittel enthaltend die nichtionisch hydrophil modifizierten Polyisocyanate sowie die mit diesen Beschichtungsmitteln beschichteten Substrate.The invention relates to a process for the production of hydrophilically modified polyisocyanates with a low content of monomeric diisocyanates, the polyisocyanates obtainable or obtained by this process and the use of these for the production of polyurethane plastics. The invention also relates to coating compositions containing the nonionically hydrophilically modified polyisocyanates and to the substrates coated with these coating compositions.
Wässrige Lacksysteme haben sich heute für verschiedene Anwendungsbereiche als umweltfreundliche Alternative zu lösemittelhaltigen Beschichtungsmitteln fest etabliert. Eine besondere Rolle als Rohstoff für qualitativ hochwertige wässrige Lacke spielen dabei hydrophil-modifizierte Polyisocyanate, da sie als wasserdispergierbare Vemetzerkomponenten die Formulierung wässriger Zweikomponenten-Polyurethan(2K-PUR)-Lacke ermöglichen. Aqueous paint systems have become firmly established for various areas of application as an environmentally friendly alternative to solvent-based coating materials. Hydrophilic-modified polyisocyanates play a special role as raw materials for high-quality water-based paints, since as water-dispersible crosslinking components they enable the formulation of water-based two-component polyurethane (2K-PUR) paints.
Eine einfache und preiswerte Methode zur Herstellung wasserdispergierbarer Polyisocyanate ist die anteilige Umsetzung hydrophober Polyisocyanate mit hydrophilen Polyetheralkoholen (siehe z. B. EP-A 0 959 087, Seite 2, Zeilen 25 - 46). Im technischen Maßstab wird diese Umsetzung üblicherweise bei Temperaturen von ca. 80 bis 130°C durchgeführt, um wirtschaftlich akzeptable Reaktionszeiten zu gewährleisten. A simple and inexpensive method for preparing water-dispersible polyisocyanates is the proportionate reaction of hydrophobic polyisocyanates with hydrophilic polyether alcohols (see, for example, EP-A 0 959 087, page 2, lines 25-46). On an industrial scale, this reaction is usually carried out at temperatures of from about 80 to 130° C. in order to ensure reaction times that are economically acceptable.
Bei der Hydrophilierung von Polyisocyanaten, die Uretdionstrukturen enthalten, kann sich in diesem Temperaturbereich allerdings deren Thermolabilität nachteilig bemerkbar machen, die zu einem deutlichen Anstieg an monomeren Diisocyanaten fuhren kann. However, when polyisocyanates containing uretdione structures are rendered hydrophilic, their thermal lability can have an adverse effect in this temperature range and can lead to a significant increase in monomeric diisocyanates.
Zukünftig werden auch hydrophile Polyisocyanate unter die von der Europäischen Chemikalienagentur (ECHA) beschlossene Beschränkung zum Umgang mit Stoffen oder Gemischen fallen, deren Gehalt an freien monomeren Diisocyanaten 0,10 Gew.-% oder mehr beträgt. Für einen sichere gewerbsmäßige Anwendung als Vemetzerkomponenten in wässrigen 2K-PUR-Lacken sind daher hydrophile Polyisocyanate mit weniger als 0,10 % an monomeren Diisocyanaten gewünscht.In the future, hydrophilic polyisocyanates will also come under the restriction imposed by the European Chemicals Agency (ECHA) on handling substances or mixtures with a content of free monomeric diisocyanates of 0.10% by weight or more. Hydrophilic polyisocyanates with less than 0.10% of monomeric diisocyanates are therefore desirable for reliable commercial use as crosslinking components in water-based 2K PUR coatings.
Die EP 3 543 270 Al betrifft ein Katalysatorsystem für Uretdiondispersionen, wobei keine hydrophilen Polyisocyanate beschrieben werden, die einen Restmonomerengehalt von unter 0,10 Gew.-%, bezogen auf den Festkörpergehalt, aufweisen. Die US 5,252,696 A und EP 0 850 896 Al beschreiben wasserdispergierbare Polyisocyanate, ohne beispielsweise auf den Restmonomerengehalt einzugehen. Die WO2016/146474 Al offenbart Silangruppen enthaltende Polyisocyanate, die in organischen Lösemitteln vorliegen. EP 3 543 270 A1 relates to a catalyst system for uretdione dispersions, in which no hydrophilic polyisocyanates are described which have a residual monomer content of less than 0.10% by weight, based on the solids content. US Pat. No. 5,252,696 A and EP 0 850 896 A1 describe water-dispersible polyisocyanates without going into detail, for example, about the residual monomer content. WO2016/146474 A1 discloses polyisocyanates containing silane groups which are present in organic solvents.
Die EP 3 428 207 Al beschreibt hydrophile Polyisocyanatzusammensetzungen mit speziellen Verhältnissen an Uretonimin- und Iminooxadiazindiongruppen, jeweils bezogen auf die vorhandenen Isocyanuratgruppen, woraus sich ein Verhältnis von Uretonimin- zu Uretdiongruppen von 0,20 bis 50 mol-% ergibt. Die Uretonimingruppen werden hier absichtlich durch Erhitzen der Polyisocyanate vor der Hydrophilierungsreaktion gebildet. Nachteilig hieran ist, dass die thermisch
labilen Uretonimingruppen zwingend vorhanden sein müssen und nicht gewährleistet ist, dass der Gehalt an monomeren Diisocyanaten zuverlässig unter 0,10 Gew-% gehalten werden kann. EP 3 428 207 A1 describes hydrophilic polyisocyanate compositions with specific ratios of uretonimine and iminooxadiazinedione groups, based in each case on the isocyanurate groups present, resulting in a ratio of uretonimine to uretdione groups of 0.20 to 50 mol %. Here the uretonimine groups are intentionally formed by heating the polyisocyanates prior to the hydrophilization reaction. The disadvantage of this is that the thermal labile uretonimine groups must be present and there is no guarantee that the content of monomeric diisocyanates can be reliably kept below 0.10% by weight.
Allerdings können auch bereits sehr geringe Mengen an Uretdionstrukturen in einem hydrophoben Polyisocyanat während der Umsetzung mit hydrophilen Polyetheralkoholen unter den üblichen Bedingungen durch Rückspaltung den Monomergehalt auf Werte deutlich größer als 0,10 Gew.-% steigen lassen, selbst wenn das hydrophobe Polyisocyanat anfangs einen Diisocyanatgehalt von weniger als 0,10 Gew.-% aufwies. However, even very small amounts of uretdione structures in a hydrophobic polyisocyanate can cause the monomer content to rise to values significantly greater than 0.10% by weight during the reaction with hydrophilic polyether alcohols under the usual conditions by cleavage, even if the hydrophobic polyisocyanate initially has a diisocyanate content less than 0.10% by weight.
Aufgabe der vorliegenden Erfindung war es daher ein neues Verfahren zur Herstellung nichtionisch hydrophil modifizierter Polyisocyanate zur Verfügung zu stellen, nach dem sich auch Uretdionstrukturen und gegebenfalls Uretonimingruppen aufweisende hydrophobe Polyisocyanate mit hydrophilen Polyetheralkoholen umsetzen lassen, ohne dass es aufgrund von Uretdionspaltung und Uretoniminspaltung zu einem merklichen Anstieg an monomeren Diisocyanaten über 0,10 Gew.-% kommt. The object of the present invention was therefore to provide a new process for preparing nonionically hydrophilically modified polyisocyanates, according to which uretdione structures and optionally hydrophobic polyisocyanates containing uretonimine groups can also be reacted with hydrophilic polyether alcohols without a noticeable increase due to uretdione cleavage and uretonimine cleavage of monomeric diisocyanates above 0.10% by weight.
Diese Aufgabe konnte mit der Bereitstellung des nachstehend näher beschriebenen Verfahrens gelöst werden. Das erfindungsgemäße Verfahren basiert auf der überraschenden Beobachtung, dass die Tendenz zur Uretdionspaltung sowie Uretoniminspaltung und damit der Anstieg des Gehaltes an monomeren Diisocyanaten in hohem Maße mit der Qualität der eingesetzten Polyetheralkohole korreliert. Üblicherweise werden die zur Polyisocyanat-Hydrophilierung eingesetzten Polyetheralkohole durch Alkali-katalysierte Addition von Alkylenoxiden, insbesondere Ethylenoxid, an Startermoleküle mit mindestens einem aktiven Wasserstoffatom hergestellt. Im Anschluss an die Additionsreaktion wird der alkalische Katalysator dann im Allgemeinen mit einer anorganischen oder organischen Säure neutralisiert und das sich dabei bildende Salz aus dem Polyetheralkohol entfernt. Wie jetzt überraschenderweise gefunden wurde, führt die Umsetzung von Uretdiongruppen und gegebenfalls Uretonimingruppen enthaltenden Polyisocyanaten mit hydrophilen Polyetheralkoholen, die mit Phosphorsäure oder Phosphorsäureestem neutralisiert wurden zu einem deutlichen Anstieg an monomeren Diisocyanaten, während bei der Umsetzung mit phosphorfreien Polyetheralkoholen oder solchen, die weniger als 50 ppm an Phosphor aufweisen, keine Uretdionspaltung und Uretoniminspaltung zu beobachten ist. It was possible to solve this problem by providing the method described in more detail below. The process according to the invention is based on the surprising observation that the tendency towards uretdione cleavage and uretonimine cleavage and thus the increase in the content of monomeric diisocyanates correlates to a high degree with the quality of the polyether alcohols used. The polyether alcohols used for hydrophilizing polyisocyanates are usually prepared by alkali-catalyzed addition of alkylene oxides, in particular ethylene oxide, onto starter molecules having at least one active hydrogen atom. Following the addition reaction, the alkaline catalyst is then generally neutralized with an inorganic or organic acid and the salt that forms is removed from the polyether alcohol. As has now surprisingly been found, the reaction of polyisocyanates containing uretdione groups and optionally uretonimine groups with hydrophilic polyether alcohols which have been neutralized with phosphoric acid or phosphoric acid esters leads to a significant increase in monomeric diisocyanates, while the reaction with phosphorus-free polyether alcohols or those containing less than 50 ppm have phosphorus, no uretdione cleavage and uretonimine cleavage is observed.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung hydrophil modifizierter Polyisocyanate mit einem Gehalt an monomeren Diisocyanaten von weniger als 0,10 Gew.-%, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, umfassend eine Umsetzung von The present invention relates to a process for the preparation of hydrophilically modified polyisocyanates containing less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, comprising a reaction of
A) mindestens einer Polyisocyanatkomponente mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen, die mindestens Uretdionstrukturen und
weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen auf weist, mit A) at least one polyisocyanate component having aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups which have at least uretdione structures and less than 0.20 mol % of uretonimine structures based on the uretdione structures
B) mindestens einer nichtionisch hydrophilen organischen Verbindung, die mindestens eine gegenüber Isocyanaten reaktive Gruppe aufweist, wobei die nichtionisch hydrophile organische Verbindung B) einen Gehalt an Phosphor von höchstens 50 ppm aufweist, und der Gesamtgehalt an Phosphor bezogen auf die Komponenten A) und B) des hydrophil modifizierten Polyisocyanats höchstens 20 ppm beträgt. B) at least one nonionic hydrophilic organic compound which has at least one isocyanate-reactive group, the nonionic hydrophilic organic compound B) having a phosphorus content of at most 50 ppm, and the total phosphorus content based on components A) and B) of the hydrophilically modified polyisocyanate is at most 20 ppm.
Gegenstände der Erfindung sind auch nichtionisch hydrophil modifizierte Polyisocyanate, die Uretdionstrukturen und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und höchstens 20 ppm an Phosphor aufweisen, sowie ihre Verwendung als Ausgangskomponenten bei der Herstellung von Polyurethankunststoffen, insbesondere als Vernetzer für wasserlösliche oder -dispergierbare Eackbindemittel oder Eackbindemittelkomponenten mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen bei der Herstellung von Überzügen unter Verwendung von wässrigen Beschichtungsmitteln auf Basis derartiger Bindemittel oder Bindemittelkomponenten. The invention also relates to nonionically hydrophilically modified polyisocyanates containing uretdione structures and less than 0.20 mol % of uretonimine structures, based on the uretdione structures, and less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates , and have a maximum of 20 ppm of phosphorus, and their use as starting components in the production of polyurethane plastics, in particular as crosslinkers for water-soluble or water-dispersible binders or binder components with isocyanate-reactive groups in the production of coatings using aqueous coating compositions based on such binders or binder components.
Bevorzugt bedeuten erfindungsgemäß die Ausdrücke „umfassend“ oder „enthaltend“, „im Wesentlichen bestehend aus“ und besonders bevorzugt „bestehend aus“. Die in den Patentansprüchen und in der Beschreibung genannten weiteren Ausführungsformen können beliebig kombiniert werden, sofern sich aus dem Kontext nicht eindeutig das Gegenteil ergibt. According to the invention, the expressions “comprising” or “containing” preferably mean “consisting essentially of” and particularly preferably “consisting of”. The further embodiments mentioned in the patent claims and in the description can be combined as desired, provided the context does not clearly indicate the opposite.
Eine „organische Verbindung“ oder „organischer Rest“ enthält mindestens eine Einheit, die eine kovalente Kohlenstoff-Wasserstoff-Bindung umfasst. An "organic compound" or "organic radical" contains at least one moiety that comprises a covalent carbon-hydrogen bond.
Vorliegend ist der Begriff "aliphatisch" definiert als nicht-aromatische Kohlenwasserstoffgruppen, die gesättigt oder ungesättigt sind. As used herein, the term "aliphatic" is defined as non-aromatic hydrocarbon groups that are saturated or unsaturated.
Vorliegend ist der Begriff "araliphatisch" definiert als Kohlenwasserstoffreste, die sowohl aus einer aromatischen als auch aus einer gesättigten oder ungesättigten Kohlenwasserstoffgruppe bestehen, die direkt an den aromatischen Rest gebunden ist. As used herein, the term "araliphatic" is defined as hydrocarbon radicals consisting of both an aromatic and a saturated or unsaturated hydrocarbon group bonded directly to the aromatic radical.
Vorliegend ist der Begriff "alicyclisch" oder "cycloaliphatisch" definiert als gegebenenfalls substituierte, carbocyclische oder heterocyclische Verbindungen oder Einheiten, die nicht aromatisch sind. As used herein, the term "alicyclic" or "cycloaliphatic" is defined as an optionally substituted carbocyclic or heterocyclic compound or moiety that is not aromatic.
Vorliegend ist der Begriff "hydrophil" definiert als eine Wasserlöslichkeit einer Verbindung von mindestens 500 g / Liter, vorzugsweise eine vollständige Wasserlöslichkeit, und der Begriff "hydrophob" als eine Wasserlöslichkeit einer Verbindung von höchstens 100 g / Liter, vorzugsweise eine vollständige Unlöslichkeit in Wasser, jeweils bestimmt bei 20°C.
„Mindestens ein“, wie hierin verwendet, bezieht sich auf 1 oder mehr, beispielsweise 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Im Zusammenhang mit Bestandteilen der hierin beschriebenen Verbindungen bezieht sich diese Angabe nicht auf die absolute Menge an Molekülen, sondern auf die Art des Bestandteils. „Mindestens einer nichtionisch hydrophilen organischen Verbindung“ bedeutet daher beispielsweise, dass nur eine Art von Verbindung oder mehrere verschiedene Arten von Verbindungen dieser Art, ohne Angaben über die Menge der einzelnen Verbindungen zu machen, enthalten sein können. Here the term "hydrophilic" is defined as a water solubility of a compound of at least 500 g/litre, preferably complete water solubility, and the term "hydrophobic" as a water solubility of a compound of at most 100 g/litre, preferably complete insolubility in water, each determined at 20°C. "At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compounds described herein, this specification does not refer to the absolute amount of molecules, but to the type of component. "At least one non-ionic hydrophilic organic compound" therefore means, for example, that only one type of compound or several different types of compounds of this type can be present, without providing information about the amount of the individual compounds.
Numerische Bereiche, die in dem Format „in/von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden. Numerical ranges given in the format "in/from x to y" are inclusive of the stated values. When multiple preferred numeric ranges are given in this format, it is understood that all ranges given by the combination of the different endpoints arise, are also recorded.
Geeignete Polyisocyanate A) für das erfindungsgemäße Verfahren sind beliebige, durch Modifizierung einfacher aliphatischer, cycloaliphatischer, araliphatischer und/oder aromatischer Diisocyanate hergestellte Polyisocyanate, die mindestens Uretdionstrukturen aufweisen. Suitable polyisocyanates A) for the process according to the invention are any polyisocyanates which have been prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates and have at least uretdione structures.
Geeignete Diisocyanate zur Herstellung der Polyisocyanate A) können auf verschiedene Weise, beispielsweise durch Phosgenierung der korrespondierenden Diamine in der Flüssig- oder Gasphase oder auf phosgenfreien Weg, wie z. B. durch thermische Urethanspaltung, erhalten werden. Bevorzugte Diisocyanate sind solche des Molekulargewichtsbereichs 140 bis 400 mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatischgebundenen Isocyanatgruppen, wie z. B. 1,4- Diisocyanatobutan, 1,5-Diisocyanatopentan (PDI), 1,6-Diisocyanatohexan (HDI), 2-Methyl-l,5- diisocyanatopentan, l,5-Diisocyanato-2,2-dimethylpentan, 2,2,4- bzw. 2,4,4-Trimethyl-l,6- diisocyanatohexan, 1,10-Diisocyanatodecan, 1,3- und 1,4-Diisocyanatocyclohexan, 1,3- und 1,4- Bis-(isocyanatomethyl)-cyclohexan, l-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan (Isophorondiisocyanat, IPDI), 2,4‘- und 4,4'-Diisocyanatodicyclohexylmethan, 1-Isocyanato-l- methyl-4(3)isocyanato-methylcyclohexan, Bis-(isocyanatomethyl)-norboman, 1,3- und 1,4- Bis(isocyanatomethyl)benzol (Xylylendiisocyanat, XDI), 1,3- und l,4-Bis(2-isocyanatopropan-2- yl)benzol (Tetramethylxylylendiisocyanat, TMXDI), 2,4- und 2,6-Diisocyanatotoluol (TDI), 2,4'- und 4,4'-Diisocyanatodiphenylmethan (MDI), 1,5-Diisocyanatonaphthalin oder Mischungen aus mindestens zwei solcher Diisocyanate. Suitable diisocyanates for preparing the polyisocyanates A) can be used in various ways, for example by phosgenation of the corresponding diamines in the liquid or gas phase or in a phosgene-free way, such as. B. by thermal urethane cleavage. Preferred diisocyanates are those in the molecular weight range from 140 to 400 with aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanate groups, such as, for example, B. 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2, 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl )-cyclohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane, 1-isocyanato-l-methyl-4(3) isocyanato-methylcyclohexane, bis(isocyanatomethyl)norbomane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl). )benzene (tetramethylxylylene diisocyanate, TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatonaphthalene or mixtures of at least two such diisocyanates .
Neben Uretdionstrukturen können die beim erfmdungsgemäßen Verfahren eingesetzten Polyisocyanate A) gegebenenfalls zusätzlich auch Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen aufweisen. In addition to uretdione structures, the polyisocyanates A) used in the process according to the invention may also optionally have isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures.
Die Herstellung der Polyisocyanate A) erfolgt nach an sich bekannten Methoden, wie sie beispielsweise in J. Prakt. Chem. 336 (1994) 185 - 200, in 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 und DE-A 3 928
503 oder in 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 und EP-A 3 337 836 beispielhaft beschrieben sind. The polyisocyanates A) are prepared by methods known per se, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, in 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 and DE-A 3 928 503 or in 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 and EP-A 3,337,836 are described by way of example.
Bei der Herstellung dieser Polyisocyanate A) schließt sich an die eigentliche Modifizierungsreaktion in der Regel ein weiterer Verfahrensschritt zur Abtrennung der nicht umgesetzten überschüssigen monomeren Diisocyanate an. Diese Monomerenabtrennung erfolgt nach an sich bekannten Verfahren vorzugsweise durch Dünnschichtdestillation im Vakuum oder durch Extraktion mit geeigneten gegenüber Isocyanatgruppen inerten Lösungsmitteln, beispielsweise aliphatischen oder cycloaliphatischen Kohlenwasserstoffen wie Pentan, Hexan, Heptan, Cyclopentan oder Cyclohexan.In the production of these polyisocyanates A), the actual modification reaction is generally followed by a further process step for separating off the unreacted excess monomeric diisocyanates. This removal of monomers is carried out by methods known per se, preferably by thin-layer distillation in vacuo or by extraction with suitable solvents which are inert towards isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
Bevorzugt kommen beim erfindungsgemäßen Verfahren Polyisocyanate A) zum Einsatz, die einen Gehalt an monomeren Diisocyanaten von weniger als 0,14 Gew.-%, vorzugsweise weniger als 0,12 Gew.-%, besonders bevorzugt von weniger als 0,10 Gew.-% aufweisen. Die Rest-Monomeren Gehalte werden nach DIN EN ISO 10283:2007-11 gaschromatographisch mit internem Standard bestimmt. In the process according to the invention, preference is given to using polyisocyanates A) which have a monomeric diisocyanate content of less than 0.14% by weight, preferably less than 0.12% by weight, particularly preferably less than 0.10% by weight. % exhibit. The residual monomer content is determined according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard.
Abhängig von ihrem jeweiligen Herstellverfahren können die beim erfindungsgemäßen Verfahren eingesetzten Polyisocyanatkomponente A) gegebenenfalls Phosphor in einer Menge von bis zu 28 ppm, vorzugsweise bis zu 25 ppm, besonders bevorzugt bis zu 20 ppm enthalten, der beispielsweise in Form abgestoppter Oligomerisierungskatalysatoren vorliegt. Die Bestimmung dieser Phosphorgehalte erfolgt im Rahmen der vorliegenden Erfindung durch induktiv gekoppelte Plasma- Atom-Emissionsspektrometrie (ICP-OES) nach DIN EN ISO 11885:2009-09 nach Mikrowellenaufschluss. Die Nachweisgrenze für Phosphor liegt bei diesem Verfahren bei <1 ppm.Depending on their particular production process, the polyisocyanate component A) used in the process according to the invention can optionally contain phosphorus in an amount of up to 28 ppm, preferably up to 25 ppm, particularly preferably up to 20 ppm, which is present, for example, in the form of blocked oligomerization catalysts. Within the scope of the present invention, these phosphorus contents are determined by inductively coupled plasma atomic emission spectrometry (ICP-OES) in accordance with DIN EN ISO 11885:2009-09 after microwave digestion. The detection limit for phosphorus with this method is <1 ppm.
In den Polyisocyanaten A) sind Uretdionstrukturen vorhanden, vorzugsweise beträgt der Gehalt an Uretdionstrukturen mindestens 0,6 mol-%, stärker bevorzugt von 0,8 bis 25 mol-%, besonders bevorzugt von 1 bis 20 mol-%, ganz besonders bevorzugt von 1 bis 15 mol-%, jeweils bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wobei die Gesamtmenge aller im Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt. Der Gehalt an Uretoniminstrukturen in den Polyisocyanaten A) beträgt, falls überhaupt nachweisbar, weniger als 0,20 mol-%, bevorzugt weniger als 0,15 mol-%, besonders bevorzugt weniger als 0,10 mol-% bezogen auf die Uretdionstrukturen. In the polyisocyanates A) uretdione structures are present, the content of uretdione structures is preferably at least 0.6 mol %, more preferably from 0.8 to 25 mol %, particularly preferably from 1 to 20 mol %, very particularly preferably from 1 up to 15 mol %, in each case based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate, the total amount of all iminooxadiazinedione, uretdione, Isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures yields 100 mol%. The content of uretonimine structures in the polyisocyanates A), if detectable at all, is less than 0.20 mol %, preferably less than 0.15 mol %, particularly preferably less than 0.10 mol %, based on the uretdione structures.
Die Gehalte (mol-%) der in den Polyisocyanaten A) vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen werden aus den Integralen protonenentkoppelter 13C-NMR-Spektren errechnet und beziehen sich jeweils auf die Summe an vorliegenden Uretdion-, Isocyanurat-,
Allophanat-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen. Die Gehalte (mol-%) an gegebenenfalls in den Polyisocyanaten A) vorliegenden Uretonimistrukturen wurden ebenfalls aus den Integralen der protonenentkoppelten 13C-NMR-Spektren errechnet und beziehen sich auf Uretdionstrukturen. Im Falle von in CDCh gelösten HDI-Polyisocyanaten weisen die einzelnen Strukturelemente folgende chemische Verschiebungen (in ppm) auf: Uretdion: 157.1; Isocyanurat: 148.4; Iminooxadiazindion: 147.8, 144.3 und 135.3; Allophanat: 155.7 und 153.8, Biuret: 155,5; Urethan: 156,3; Oxadiazintrion: 147,8 und 143,9; Uretonimin: 158,7 und 144,6. The contents (mol %) of the uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanates A) are calculated from the integrals of proton-decoupled 13 C-NMR spectra and relate based on the total of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures. The contents (mol %) of any uretonime structures present in the polyisocyanates A) were also calculated from the integrals of the proton-decoupled 13 C-NMR spectra and relate to uretdione structures. In the case of HDI polyisocyanates dissolved in CDCh, the individual structural elements have the following chemical shifts (in ppm): uretdione: 157.1; Isocyanurate: 148.4; iminooxadiazinedione: 147.8, 144.3 and 135.3; allophanate: 155.7 and 153.8, biuret: 155.5; urethane: 156.3; oxadiazinetrione: 147.8 and 143.9; Uretonimine: 158.7 and 144.6.
Geeignete Polyisocyanate A) sind auch beliebige Mischungen aus mindesten zwei Polyisocyanaten der genannten Art, wobei in diesen Mischungen auch solche Polyisocyanate zum Einsatz gelangen können, die völlig frei von Uretdionstrukturen sind, sofern die Mischungen den vorstehend für die Polyisocyanate A) gemachten Angaben bezüglich der Gehalte an Uretdion- und Uretoniminstrukturen entsprechen. Suitable polyisocyanates A) are also any mixtures of at least two polyisocyanates of the type mentioned, in which case polyisocyanates which are completely free of uretdione structures can also be used in these mixtures, provided the mixtures have the information given above for the polyisocyanates A) with regard to the contents correspond to uretdione and uretonimine structures.
Bevorzugte Polyisocyanate A) sind solche der genannten Art, die neben Uretdionstrukturen zusätzlich mindestens Isocyanuratstrukturen enthalten. Preferred polyisocyanates A) are those of the type mentioned which, in addition to uretdione structures, also contain at least isocyanurate structures.
Polyisocyanate mit araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen werden beim erfmdungsgemäßen Verfahren, falls überhaupt, vorzugsweise in Mengen von höchstens 20 Gew.-%, besonders bevorzugst von höchsten 10 Gew.-%, bezogen auf die Gesamtmenge an Polyisocyanaten A) mitverwendet. Besonders bevorzugte Polyisocyanate A) für das erfmdungsgemäße Verfahren sind solche der genannten Art mit ausschließlich aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen, die frei von Uretonimingruppen sind bzw. in denen Uretonimingruppen nicht nachweisbar sind. Polyisocyanates with araliphatically and/or aromatically bound isocyanate groups are used in the process according to the invention, if at all, preferably in amounts of at most 20% by weight, particularly preferably at most 10% by weight, based on the total amount of polyisocyanates A). Particularly preferred polyisocyanates A) for the process according to the invention are those of the type mentioned with exclusively aliphatically and/or cycloaliphatically bound isocyanate groups which are free of uretonimine groups or in which uretonimine groups are not detectable.
Ganz besonders bevorzugte Polyisocyanate A) sind solche auf Basis von PDI, HDI, IPDI und/oder 2,4‘- und 4,4'-Diisocyanatodicyclohexylmethan. Very particularly preferred polyisocyanates A) are those based on PDI, HDI, IPDI and/or 2,4'- and 4,4'-diisocyanatodicyclohexylmethane.
Die vorstehend als geeignet, bevorzugt, besonders bevorzugt und ganz besonders bevorzugt genannten Polyisocyanate A) enthalten Uretdionstrukturen und gegebenenfalls vorzugsweise Isocyanuratstrukturen und weisen eine mittlere NCO-Funktionalität von 2,3 bis 5,0, vorzugsweise von 2,5 bis 4,5, sowie einen Gehalt an Isocyanatgruppen von 6,0 bis 26,0 Gew.-%, vorzugsweise von 8,0 bis 25,0 Gew.-%, besonders bevorzugt 10,0 bis 24,0 Gew.-% auf. The polyisocyanates A) mentioned above as being suitable, preferred, particularly preferred and very particularly preferred contain uretdione structures and, if appropriate, preferably isocyanurate structures, and have an average NCO functionality of from 2.3 to 5.0, preferably from 2.5 to 4.5, and an isocyanate group content of from 6.0 to 26.0% by weight, preferably from 8.0 to 25.0% by weight, particularly preferably from 10.0 to 24.0% by weight.
Ausgangsverbindungen B) für das erfmdungsgemäße Verfahren sind beliebige nichtionisch hydrophile organische Verbindungen mit mindestens einer gegenüber Isocyanaten reaktiven Gruppe, die einen Gehalt an Phosphor von höchstens 50 ppm aufweisen. Vorzugsweise sind die in WO 2016/146474 Al explizit genannten, gegenüber Isocyanatgruppen reaktiven Silanverbindungen ausgenommen von den Ausgangsverbindungen B) der vorliegenden Erfindung. Starting compounds B) for the process according to the invention are any nonionic hydrophilic organic compounds which have at least one isocyanate-reactive group and which have a phosphorus content of at most 50 ppm. The silane compounds which are reactive toward isocyanate groups and are explicitly mentioned in WO 2016/146474 A1 are preferably excluded from the starting compounds B) of the present invention.
Geeignete Ausgangsverbindungen B) sind beispielsweise ein- oder mehrwertige, im statistischen Mittel 5 bis 50 Ethylenoxideinheiten pro Molekül aufweisende Polyalkylenoxidpolyetheralkohole,
wie sie in an sich bekannter Weise durch Alkoxylierung geeigneter Startermoleküle zugänglich sind (siehe z. B. Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Band 19, Verlag Chemie, Weinheim S. 31 - 38). Solche Startermoleküle können beispielsweise beliebige ein- oder mehrwertige Alkohole des Molekulargewichtsbereiches 32 bis 300 sein, wie z. B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, sec-Butanol, die isomeren Pentanoie, Hexanoie, Octanole und Nonanole, n-Decanol, n-Dodecanol, n-Tetradecanol, n-Hexadecanol, n-Octadecanol, Cyclohexanol, die isomeren Methylcyclohexanole, Hydroxymethylcyclohexan, 3-Methyl-3- hydroxymethyloxetan, Benzylalkohol, Phenol, die isomeren Kresole, Octylphenole, Nonylphenole und Naphthole, Furfurylalkohol, Tetrahydrofurfurylalkohol, 1,2-Ethandiol, 1,2- und 1,3-Propandiol, die isomeren Butandiole, Pentandiole, Hexandiole, Heptandiole und Octandiole, 1,2- und 1,4- Cyclohexandiol, 1,4-Cyclohexandimethanol, 4,4'-(l-Methylethyliden)-biscyclohexanol, 1,2,3- Propantriol, 1,1,1-Trimethylolethan, 1,2,6-Hexantriol, 1,1,1-Trimethylolpropan, 2,2- Bis(hydroxymethyl)-l,3-propandiol oder l,3,5-Tris(2-hydroxyethyl)isocyanurat. Suitable starting compounds B) are, for example, monohydric or polyhydric polyalkylene oxide polyether alcohols having a statistical average of 5 to 50 ethylene oxide units per molecule, as are accessible in a manner known per se by alkoxylating suitable starter molecules (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, Verlag Chemie, Weinheim, p. 31-38). Such starter molecules can be, for example, any mono- or polyhydric alcohols in the molecular weight range from 32 to 300, such as. B. methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanoic, hexanoic, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n- Octadecanol, cyclohexanol, the isomeric methylcyclohexanols, hydroxymethylcyclohexane, 3-methyl-3-hydroxymethyloxetane, benzyl alcohol, phenol, the isomeric cresols, octylphenols, nonylphenols and naphthols, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1,2-ethanediol, 1,2- and 1,3 -propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-(1-methylethylidene)biscyclohexanol, 1,2,3 - propane triol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis(hydroxymethyl)-l,3-propanediol or l,3,5-tris( 2-hydroxyethyl) isocyanurate.
Für die Alkoxylierungsreaktion geeignete Alkylenoxide sind insbesondere Ethylenoxid und Propylenoxid, die in beliebiger Reihenfolge oder auch im Gemisch bei der Alkoxylierungsreaktion eingesetzt werden können. Geeignete Polyetheralkohole sind entweder reine Polyethylenoxid- polyetheralkohole oder gemischte Polyalkylenoxidpolyether, deren Alkylenoxideinheiten zu mindestens 70 mol-%, vorzugsweise zu mindestens 80 mol-% aus Ethylenoxideinheiten bestehen.Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any order or as a mixture in the alkoxylation reaction. Suitable polyether alcohols are either pure polyethylene oxide polyether alcohols or mixed polyalkylene oxide polyethers, the alkylene oxide units of which consist of at least 70 mol %, preferably at least 80 mol %, of ethylene oxide units.
Bevorzugte Polyalkylenoxidpolyetheralkohole B) sind solche, die unter Verwendung der oben genannten Monoalkohole des Molekulargewichtsbereiches 32 bis 150 als Startermoleküle hergestellt wurden. Weiter bevorzugt handelt es sich bei der nichtionisch hydrophilen organischen Verbindung B) um ein- oder mehrwertige, im statistischen Mittel 5 bis 50 Ethylenoxideinheiten, besonders bevorzugt 5 bis 25 Ethylenoxideinheiten pro Molekül aufweisende Polyalkylenoxid- polyetheralkohole. Besonders bevorzugte Polyetheralkohole sind reine Polyethylenglycol- monomethyletheralkohole, die im statistischen Mittel 5 bis 50, ganz besonders bevorzugt 5 bis 25 Ethylenoxideinheiten aufweisen. Preferred polyalkylene oxide polyether alcohols B) are those which have been prepared using the abovementioned monoalcohols with a molecular weight in the range from 32 to 150 as starter molecules. More preferably, the nonionic hydrophilic organic compound B) is a monohydric or polyhydric polyalkylene oxide polyether alcohol having a statistical average of 5 to 50 ethylene oxide units, particularly preferably 5 to 25 ethylene oxide units, per molecule. Particularly preferred polyether alcohols are pure polyethylene glycol monomethyl ether alcohols which have a statistical average of 5 to 50, very particularly preferably 5 to 25, ethylene oxide units.
Die nichtionisch hydrophilen Verbindungen B) weisen vorzugsweise einen pH-Wert, gemessen an einer 5 %igen Lösung in Wasser, von 4,0 bis 8,0, vorzugsweise von 4,5 bis 7,5, besonders bevorzugt von 5,0 bis 7,0 auf. The nonionic hydrophilic compounds B) preferably have a pH, measured on a 5% solution in water, of 4.0 to 8.0, preferably 4.5 to 7.5, particularly preferably 5.0 to 7 ,0 on.
Die eingesetzte Menge an nichtionisch hydrophilen Verbindungen B) kann beim erfmdungsgemäßen Verfahren über einen breiten Bereich frei gewählt werden. Bevorzugt kommen nichtionisch hydrophile Verbindungen B) beim erfmdungsgemäßen Verfahren in Mengen von bis zu 30 Gew.-%, besonders bevorzugt von 2 bis 25 Gew.-%, ganz besonders bevorzugt von 5 bis 20 Gew.-% und insbesondere von 9 bis 17 Gew.-%, bezogen auf die Gesamtmenge der verwendeten Ausgangskomponenten A) und B) zum Einsatz.
Erfindungswesentlich ist, dass die nichtionisch hydrophilen Verbindungen B) einen Gehalt an Phosphor von höchstens 50 ppm, vorzugsweise von höchstens 40 ppm, besonders bevorzugt von höchstens 30 ppm und ganz besonders bevorzugt keinen nachweisbaren Phosphor aufweisen, wobei die Phosphorgehalte durch induktiv gekoppelte Plasma-Atom-Emissionsspektrometrie (ICP-OES) nach DIN EN ISO 11885:2009-09 nach Mikrowellenaufschluss bestimmt werden. Die Nachweisgrenze für Phosphor liegt bei diesem Verfahren bei <1 ppm. The amount of nonionic hydrophilic compounds B) used can be freely selected over a wide range in the process according to the invention. In the process according to the invention, nonionic hydrophilic compounds B) are preferably used in amounts of up to 30% by weight, particularly preferably from 2 to 25% by weight, very particularly preferably from 5 to 20% by weight and in particular from 9 to 17% by weight %, based on the total amount of starting components A) and B) used. It is essential to the invention that the nonionic hydrophilic compounds B) have a phosphorus content of at most 50 ppm, preferably at most 40 ppm, particularly preferably at most 30 ppm and very particularly preferably no detectable phosphorus, the phosphorus contents being determined by inductively coupled plasma atomic Emission spectrometry (ICP-OES) according to DIN EN ISO 11885:2009-09 after microwave digestion. The detection limit for phosphorus with this method is <1 ppm.
Der Gesamtgehalt an Phosphor in denn aus den Komponenten A) und B) bestehenden erfindungsgemäßen hydrophil modifizierten Polyisocyanaten, der ebenfalls nach der vorstehend beschriebenen ICP-OES-Methode bestimmt werden kann, beträgt höchstens 20 ppm, vorzugsweise von 3 bis 19 ppm, besonders bevorzugt von 5 bis 18 ppm. The total phosphorus content in the hydrophilically modified polyisocyanates according to the invention consisting of components A) and B), which can also be determined by the ICP-OES method described above, is at most 20 ppm, preferably from 3 to 19 ppm, particularly preferably from 5 to 18ppm.
Der Gesamtgehalt an Phosphor in den erfindungsgemäßen hydrophil modifizierten Polyisocyanaten kann aber auch auf einfache Weise aus den Phosphorgehalten der Polyisocyanatkomponenten A) und der hydrophilen Verbindungen B) rechnerisch ermittelt werden. In die Berechnung des Gesamtgehaltes an Phosphor gehen dabei auch die Mengen an Phosphor mit ein, die beim erfindungsgemäßen Verfahren gegebenenfalls in Form saurer Phosphorverbindungen der Polyisocyanatkomponente A) und/oder der nichtionisch hydrophilen organischen Verbindung B) vor und/oder während der Umsetzung zur Stabilisierung oder Neutralisation basischer Katalysatorreste zugesetzt werden. However, the total phosphorus content in the hydrophilically modified polyisocyanates according to the invention can also be determined by calculation in a simple manner from the phosphorus contents of the polyisocyanate components A) and the hydrophilic compounds B). The calculation of the total phosphorus content also includes the amounts of phosphorus which, in the process according to the invention, may be present in the form of acidic phosphorus compounds of the polyisocyanate component A) and/or the nonionic hydrophilic organic compound B) before and/or during the reaction for stabilization or Neutralization of basic catalyst residues are added.
Solche sauren Phosphorverbindungen sind beispielsweise Phosphorsäure, Phosphorsäureester, wie z. B. Methylphosphat, Ethylphosphat, n-Butylphosphat, n-Hexylphosphat, 2-Ethylhexylphosphat, Isooctylphosphat, n-Dodecylphosphat, Dimethylphosphat, Diethylphosphat, Di-n-propylphosphat, Di-n-butylphosphat, Di-n-amylphosphat, Disoamylphosphat, Di-n-decylphosphat, Diphenylphosphat und Dibenzylphosphat, und/oder Phosphonsäureester, wie z. B. Methylphosphonat, Ethylphosphonat, iso-Propylphosphonat, n-Propylphosphonat, n- Butylphosphonat, iso-Butylphosphonat, sek-Butylphosphonat, tert-Butylphosphonat, n- Hexylphosphonat, n-Heptylphosphonat, n-Octylphosphonat, n-Decylphosphonat, n- Dodecylphosphonat, 2-Ethylhexylphosphonat und 2-Propylheptylphosphonat. Such acidic phosphorus compounds are, for example, phosphoric acid, phosphoric acid esters, such as. B. Methyl phosphate, ethyl phosphate, n-butyl phosphate, n-hexyl phosphate, 2-ethylhexyl phosphate, isooctyl phosphate, n-dodecyl phosphate, dimethyl phosphate, diethyl phosphate, di-n-propyl phosphate, di-n-butyl phosphate, di-n-amyl phosphate, disoamyl phosphate, di- n-decyl phosphate, diphenyl phosphate and dibenzyl phosphate, and/or phosphonic acid esters, such as e.g. B. methyl phosphonate, ethyl phosphonate, iso-propyl phosphonate, n-propyl phosphonate, n-butyl phosphonate, iso-butyl phosphonate, sec-butyl phosphonate, tert-butyl phosphonate, n-hexyl phosphonate, n-heptyl phosphonate, n-octyl phosphonate, n-decyl phosphonate, n- dodecyl phosphonate, 2-ethylhexylphosphonate and 2-propylheptylphosphonate.
Das erfindungsgemäße Verfahren wird vorzugsweise lösemittelfrei durchgefiihrt. Gegebenenfalls können aber auch geeignete, gegenüber den reaktiven Gruppen der Ausgangskomponenten, insbesondere gegenüber Isocyanatgruppen inerte Lösemittel mitverwendet werden. Geeignete Lösemittel sind beispielsweise die an sich bekannten üblichen Lacklösemittel, wie z. B. Ethylacetat, Butylacetat, Ethylenglykolmonomethyl- oder -ethyletheracetat, 1 -Methoxypropyl -2 -acetat, 3-Methoxy-n-butylacetat, Aceton, 2-Butanon, 4-Methyl -2 -pentanon, Cyclohexanon, Toluol, Xylol, Chlorbenzol, Testbenzin, höher substituierte Aromaten, wie sie beispielsweise unter den Bezeichnungen Solventnaphtha, Solvesso®, Isopar®, Nappar® (Deutsche EXXON CHEMICAL GmbH, Köln, DE) und Shellsol® (Deutsche Shell Chemie GmbH, Eschborn, DE) im Handel sind,
Kohlensäureester, wie Dimethylcarbonat, Diethylcarbonat, 1,2-Ethylencarbonat und 1,2-Propylen- carbonat, Lactone, wie ß-Propiolacton, y-Butyrol acton, E-Caprolacton und e-Methylcaprolacton, aber auch Lösemittel wie Propylenglykoldiacetat, Diethylenglykoldimethylether, Dipropylenglykoldimethylether, Butylglykolacetat, Butyldiglykolacetat, 1,3-Dioxolan, N-Methylpyrrolidon und N- Methylcaprolactam, oder beliebige Gemische solcher Lösemittel. The process according to the invention is preferably carried out without solvents. If appropriate, however, suitable solvents which are inert towards the reactive groups of the starting components, in particular towards isocyanate groups, can also be used. Suitable solvents are, for example, the conventional paint solvents known per se, such as e.g. ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, 1-methoxypropyl -2 -acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl -2 -pentanone, cyclohexanone, toluene, xylene, chlorobenzene, White spirit, higher-substituted aromatics, such as those commercially available under the names Solventnaphtha, Solvesso®, Isopar®, Nappar® (Deutsche EXXON CHEMICAL GmbH, Cologne, DE) and Shellsol® (Deutsche Shell Chemie GmbH, Eschborn, DE), Carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones such as ß-propiolactone, γ-butyrolactone, ε-caprolactone and ε-methylcaprolactone, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether , butyl glycol acetate, butyl diglycol acetate, 1,3-dioxolane, N-methylpyrrolidone and N-methylcaprolactam, or any mixtures of such solvents.
Zur Durchführung des erfindungsgemäßen Verfahrens werden die Ausgangskomponenten A) und B) im allgemeinen bei Temperaturen von 40 bis 180 °C, vorzugsweise 50 bis 150 °C, unter Einhaltung eines NCO/OH-Äquivalent-Verhältnisses von 2: 1 bis 400: 1, vorzugsweise von 4: 1 bis 140: 1, vorzugsweise bis zum Erreichen des theoretisch errechneten NCO-Gehalts miteinander umgesetzt, wobei der Verlauf der Umsetzung durch z. B. titrimetrische Bestimmung des NCO-Gehaltes verfolgt werden kann. Die Bestimmung des NCO-Gehaltes erfolgt vorzugsweise titrimetrisch nach DIN EN ISO 11909:2007-05. To carry out the process according to the invention, the starting components A) and B) are generally mixed at temperatures of from 40 to 180° C., preferably from 50 to 150° C., while maintaining an NCO/OH equivalent ratio of from 2:1 to 400:1, preferably from 4: 1 to 140: 1, preferably until the theoretically calculated NCO content is reached, the course of the reaction being monitored by z. B. titrimetric determination of the NCO content can be followed. The NCO content is preferably determined titrimetrically according to DIN EN ISO 11909:2007-05.
Dabei kann die Umsetzung der Polyisocyanatkomponente A) mit den nichtionisch hydrophilen Verbindungen B) beispielsweise bis zu dem einer vollständigen Urethanisierung entsprechenden NCO-Gehalt erfolgen. Diese Umsetzung kann unkatalysiert geschehen, zur Reaktionsbeschleunigung können aber auch die üblichen aus der Polyurethanchemie bekannten Urethanisierungskatalysatoren mitverwendet werden, beispielsweise tert. Amine wie Triethylamin, Pyridin, Methylpyridin, Benzyldimethylamin, N,N-Endoethylenpiperazin, N-Methylpiperidin, Pentamethyldiethylentriamin, N,N-Dimethylcyclohexylamin, N,N'-Dimethylpiperazin oder Metallsalze wie Eisen(III)-chlorid, Zinkchlorid, Zink-octoat, Zink-2-ethylcaproat, Zink-acetylacetonat, Zinn(II)-octoat, Zinn(II)-ethylcaproat, Zinn(II)-palmitat, Dibutylzinn(IV)-dilaurat, Zirconium-(IV)- 2-ethyl-l-hexanoat, Zirconium-(IV)-neodecanoat, Zirconium-(IV)-naphthenat, Zirkonium-(IV)- acetylacetonat, Aluminium-tri(ethylacetoacetat), Wismut(III)-2-ethylhexanoat, Wismut(III)-octoat, Wismut(III)-neodecanoat und Molybdänglykolat. The reaction of the polyisocyanate component A) with the nonionic hydrophilic compounds B) can be carried out, for example, up to the NCO content corresponding to complete urethanization. This reaction can take place without catalysis, but the usual urethanization catalysts known from polyurethane chemistry can also be used to accelerate the reaction, for example tert. amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N'-dimethylpiperazine or metal salts such as iron(III) chloride, zinc chloride, zinc octoate, Zinc 2-ethylcaproate, Zinc acetylacetonate, Tin(II) octoate, Tin(II) ethylcaproate, Tin(II) palmitate, Dibutyltin(IV) dilaurate, Zirconium(IV)-2-ethyl-l- hexanoate, zirconium(IV) neodecanoate, zirconium(IV) naphthenate, zirconium(IV) acetylacetonate, aluminum tri(ethylacetoacetate), bismuth(III) 2-ethylhexanoate, bismuth(III) octoate, bismuth (III) neodecanoate and molybdenum glycolate.
Diese Katalysatoren kommen gegebenenfalls in Mengen von 0,001 bis 2,0 Gew.-%, bevorzugt 0,01 bis 0,2 Gew.-%, bezogen auf die Gesamtmenge der verwendeten Ausgangskomponenten A) und B) zum Einsatz. These catalysts are used in amounts of 0.001 to 2.0% by weight, preferably 0.01 to 0.2% by weight, based on the total amount of starting components A) and B) used.
Die Umsetzung kann beispielsweise aber auch nach dem in EP-B 0 959 087 beschriebenen Verfahren so geführt werden, dass die durch NCO/OH-Reaktion primär gebildeten Urethangruppen zumindest anteilig, vorzugsweise zu mindestens 60 mol-%, zu Allophanatgruppen weiter umgesetzt werden. In diesem Fall werden Reaktionspartner im oben genannten NCO/OH-Äquivalentverhältnis bei Temperaturen von 40 bis 180 °C, vorzugsweise 50 bis 150 °C, in der Regel in Gegenwart der in der zitierten Patentschrift angeführten, zur Beschleunigung der Allophanatisierungsreaktion geeigneten Katalysatoren, insbesondere Zinkverbindungen, wie z. B. Zink-(II)-n-octanoat, Zink-(II)-2 -ethyl- 1- hexanoat oder Zink-(II)-stearat, zur Reaktion gebracht.
Diese Allophanatisierungskatalysatoren kommen gegebenenfalls in Mengen von 0,001 bis 2,0 Gew.-%, bevorzugt 0,01 bis 0,2 Gew.-%, bezogen auf die Gesamtmenge der verwendeten Ausgangskomponenten A) und B) zum Einsatz. The reaction can, for example, also be carried out according to the process described in EP-B 0 959 087 in such a way that the urethane groups primarily formed by the NCO/OH reaction are at least partially, preferably at least 60 mol %, further converted to allophanate groups. In this case, reactants are reacted in the abovementioned NCO/OH equivalent ratio at temperatures of 40 to 180° C., preferably 50 to 150° C., generally in the presence of the catalysts, in particular zinc compounds, which are suitable for accelerating the allophanatization reaction and are listed in the cited patent , such as B. zinc (II) n-octanoate, zinc (II) -2 -ethyl- 1-hexanoate or zinc (II) stearate, reacted. These allophanatization catalysts are used in amounts of 0.001 to 2.0% by weight, preferably 0.01 to 0.2% by weight, based on the total amount of starting components A) and B) used.
Bei der katalysierten Umsetzung der Komponenten A) und B) werden die eingesetzten Katalysatoren nach Erreichen des angestrebten NCO-Gehaltes in der Regel chemisch abgestoppt. Hierfür geeignete Katalysatorgifte sind beispielsweise anorganische Säuren wie Salzsäure, phosphorige Säure oder Phosphorsäure, Säurechloride wie Acetylchlorid, Benzoylchlorid oder Isophthaloyldichlorid, Sulfonsäuren und Sulfonsäureester, wie Methansulfonsäure, p-Toluolsulfonsäure, Trifluormethansulfonsäure, Perfluorbutansulfonsäure, p-Toluolsulfonsäuremethylester und -ethylester, Mono- und Dialkylphosphate wie Monotridecylphosphat, Dibutylphosphat und Dioctylphosphat, aber auch silylierte Säuren, wie Methansulfonsäuretrimethylsilylester, Trifluormethansulfonsäuretrimethylsilylester, Phosphorsäure-tris-(trimethylsilylester) und Phosphorsäurediethylester-trimethylsilylester. In the catalyzed reaction of components A) and B), the catalysts used are generally stopped chemically after the desired NCO content has been reached. Catalyst poisons suitable for this purpose are, for example, inorganic acids such as hydrochloric acid, phosphorous acid or phosphoric acid, acid chlorides such as acetyl chloride, benzoyl chloride or isophthaloyl dichloride, sulfonic acids and sulfonic acid esters such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, methyl p-toluenesulfonate and -ethyl ester, mono- and dialkyl phosphates such as Monotridecyl phosphate, dibutyl phosphate and dioctyl phosphate, but also silylated acids, such as trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, tris-(trimethylsilyl) phosphoric acid and trimethylsilyl diethyl phosphate.
Falls zur Abstoppung der gegebenenfalls beim erfindungsgemäßen Verfahren mitzuverwendenden Katalysatoren phosphorhaltige Katalysatorgifte der genannten Art eingesetzt werden, wird deren Phosphorgehalt nicht dem Gesamtgehalt an Phosphor des aus den Komponenten A) und B) bestehenden hydrophil modifizierten Polyisocyanats zugerechnet. Die Bestimmung des Gesamtgehalt an Phosphor in den erfindungsgemäßen hydrophil modifizierten Polyisocyanaten erfolgt in diesem Fall rechnerisch aus den Phosphorgehalten der Polyisocyanatkomponenten A) und der hydrophilen Verbindungen B) und gegebenenfalls beim erfindungsgemäßen Verfahren vor und/oder während der Umsetzung zur Stabilisierung oder Neutralisation basischer Katalysatorreste zugesetzter Mengen saurer Phosphorverbindungen. If phosphorus-containing catalyst poisons of the type mentioned are used to stop the catalysts that may be used in the process according to the invention, their phosphorus content is not included in the total phosphorus content of the hydrophilically modified polyisocyanate consisting of components A) and B). In this case, the total content of phosphorus in the hydrophilically modified polyisocyanates according to the invention is determined by calculation from the phosphorus contents of the polyisocyanate components A) and the hydrophilic compounds B) and, if appropriate, in the process according to the invention before and/or during the reaction for the stabilization or neutralization of basic catalyst residues added amounts acidic phosphorus compounds.
Unter Verwendung von phosphorfreien Polyetheralkoholen oder solchen, die weniger als 50 ppm an Phosphor aufweisen, liefert das erfmdungsgemäße Verfahren reproduzierbar Uretdionstrukturen und gegebenfalls Uretonimingruppen enthaltende hydrophile Polyisocyanate mit einem Gehalt an monomeren Diisocyanaten von weniger als 0,10 Gew.-%, bezogen auf den Festkörpergehalt der Uretdionstrukturen und gegebenenfalls Uretonimingruppen enthaltenden hydrophil modifizierten Polyisocyanate. Uretdionspaltung und Uretoniminspaltung tritt, falls überhaupt, in so geringen Maße auf, dass kein negativer Einfluss auf den Monomergehalt zu beobachten ist. Die nach dem erfindungsgemäßen Verfahren erhältliche oder erhaltenen nichtionisch hydrophil modifizierten Polyisocyanate sind ebenfalls Gegenstand der vorliegenden Erfindung. Using phosphorus-free polyether alcohols or those containing less than 50 ppm of phosphorus, the process according to the invention gives reproducible uretdione structures and optionally hydrophilic polyisocyanates containing uretonimine groups with a content of monomeric diisocyanates of less than 0.10% by weight, based on the solids content of hydrophilically modified polyisocyanates containing uretdione structures and optionally uretonimine groups. Cleavage of uretdione and uretonimine occurs, if at all, to such a small extent that no negative influence on the monomer content can be observed. The present invention also relates to the nonionically hydrophilically modified polyisocyanates obtainable or obtained by the process according to the invention.
Eine weitere bevorzugte Ausführungsform der Erfindung sind nichtionisch hydrophil modifizierte Polyisocyanate, die von 0,8 bis 25 mol-%, besonders bevorzugt von 1 bis 20 mol-% und ganz besonders bevorzugt von 1 bis 15 mol-% Uretdionstrukturen, jeweils bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wobei die Gesamtmenge aller im
Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt, und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und höchstens 20 ppm an Phosphor aufweisen. A further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol %, particularly preferably from 1 to 20 mol % and very particularly preferably from 1 to 15 mol % of uretdione structures, based in each case on the total amount all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate, the total amount of all im Polyisocyanate present iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and / or oxadiazinetrione structures results in 100 mol%, and contain less than 0.20 mol% of uretonimine structures based on the uretdione structures and less than 0, 10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and not more than 20 ppm of phosphorus.
Eine weitere bevorzugte Ausführungsform der Erfindung sind nichtionisch hydrophil modifizierte Polyisocyanate, die von 0,8 bis 25 mol-% Uretdionstrukturen, bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wobei die Gesamtmenge aller im Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt, und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und von 3 bis 19 ppm, bevorzugt von 5 bis 18 ppm, an Phosphor aufweisen. A further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol % uretdione structures, based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mole %, and less than 0.20 mole % based on uretonimine structures on the uretdione structures and contain less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and from 3 to 19 ppm, preferably from 5 to 18 ppm, of phosphorus.
Eine weitere bevorzugte Ausführungsform der Erfindung sind nichtionisch hydrophil modifizierte Polyisocyanate, die von 0,8 bis 25 mol-% Uretdionstrukturen, bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wobei die Gesamtmenge aller im Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt, und weniger als 0,15 mol-%, bevorzugt weniger als 0,10 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und höchstens 20 ppm an Phosphor aufweisen und wobei der Gehalt an Uretoniminstrukturen besonders bevorzugt unterhalb der Nachweisgrenze hegt. A further preferred embodiment of the invention are nonionically hydrophilically modified polyisocyanates which contain from 0.8 to 25 mol % uretdione structures, based on the total amount of all uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mole %, and less than 0.15 mole %, preferably less than 0.10 mol % of uretonimine structures based on the uretdione structures and less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and at most 20 ppm of phosphorus and the content of uretonimine structures particularly preferably below the detection limit.
Eine weitere bevorzugte Ausführungsform der Erfindung sind Polyether modifizierte Polyisocyanate, die von 0,8 bis 25 mol-% Uretdionstrukturen, bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wobei die Gesamtmenge aller im Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt, und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und höchstens 20 ppm an Phosphor aufweisen, erhältlich oder erhalten durch Umsetzung von wenigstens einer Polyisocyanatkomponente A) auf Basis von PDI und/oder HDI mit
B) mindestens eines Polyethylenglycolmonomethyletheralkohols, der im statistischen Mittel 5 bis 25 Ethylenoxideinheiten aufweist. Another preferred embodiment of the invention are polyether-modified polyisocyanates, the 0.8 to 25 mol% uretdione, based on the total amount of all present in the polyisocyanate uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and /or oxadiazinetrione structures wherein the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate is 100 mol%, and less than 0.20 mol% of uretonimine structures based on which contain uretdione structures and have less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and at most 20 ppm of phosphorus, obtainable or obtained by reacting at least one polyisocyanate component A) based on PDI and /or HDI with B) at least one polyethylene glycol monomethyl ether alcohol which has a statistical average of 5 to 25 ethylene oxide units.
Die erfindungsgemäßen hydrophilen, Uretdionstrukturen und gegebenenfalls Uretonimingruppen enthaltenden Polyisocyanate stellen wertvolle Ausgangsmaterialien zur Herstellung von Polyurethankunststoffen nach dem Isocyanat-Polyadditionsverfahren dar. The hydrophilic polyisocyanates according to the invention containing uretdione structures and optionally uretonimine groups are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process.
Hierzu werden die hydrophil modifizierten Polyisocyanate vorzugsweise in Form wäßriger Emulsionen eingesetzt, die in Kombination mit in Wasser dispergierten Polyhydroxylverbindungen im Sinne von wäßrigen Zweikomponenten-Systemen zur Umsetzung gebracht werden können. Der sehr niedrige Gehalt an monomeren Diisocyanaten von weniger als 0,10 Gew.-%, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, ermöglicht dabei dem gewerblichen Anwender eine sichere Handhabung. For this purpose, the hydrophilically modified polyisocyanates are preferably used in the form of aqueous emulsions which can be reacted in combination with water-dispersed polyhydroxyl compounds in the sense of aqueous two-component systems. The very low content of monomeric diisocyanates of less than 0.10% by weight, based on the solids content of the hydrophilically modified polyisocyanates, enables safe handling for commercial users.
Gegebenenfalls können den nach dem erfindungsgemäßen Verfahren hergestellten hydrophil modifizierten Polyisocyanate vor der Emulgierung noch weitere nichthydrophilierte Polyisocyanate mit aliphatisch, cycloaliphatisch araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen, insbesondere Lackpolyisocyanate der obengenannten Art, zugesetzt werden. In solchen Mischungen übernehmen die erfindungsgemäßen Verfahrensprodukte die Funktion eines Emulgators für den nachträglich zugemischten Anteil an nichthydrophilen Polyisocyanaten. If desired, other non-hydrophilic polyisocyanates having aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups, in particular paint polyisocyanates of the type mentioned above, can be added to the hydrophilically modified polyisocyanates prepared by the process according to the invention before emulsification. In such mixtures, the products of the process according to the invention assume the function of an emulsifier for the proportion of non-hydrophilic polyisocyanates which is added subsequently.
Besonders bevorzugt werden die erfindungsgemäßen nichtionisch hydrophil modifizierten Polyiso- cyanatgemische als Vernetzer für in Wasser gelöste oder dispergierte Lackbindemittel oder Lackbindemittelkomponenten mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen, insbesondere alkoholischen Hydroxylgruppen, bei der Herstellung von Beschichtungen unter Verwendung von wäßrigen Beschichtungsmitteln auf Basis derartiger Bindemittel bzw. Bindemittelkomponenten verwendet. Die Vereinigung des Vernetzers, gegebenenfalls in emulgierter Form, mit den Bindemitteln bzw. Bindemittelkomponenten kann hierbei durch einfaches Verrühren vor der Verarbeitung der Beschichtungsmittel nach beliebigen Methoden oder auch unter Verwendung von Zweikomponenten- Spritzpistolen erfolgen. The nonionically hydrophilically modified polyisocyanate mixtures according to the invention are particularly preferably used as crosslinking agents for paint binders or paint binder components dissolved or dispersed in water with isocyanate-reactive groups, in particular alcoholic hydroxyl groups, in the production of coatings using aqueous coating compositions based on such binders or binder components . The crosslinking agent, optionally in emulsified form, can be combined with the binders or binder components by simple stirring before the coating compositions are processed, using any desired method, or using two-component spray guns.
In diesem Zusammenhang seien als Lackbindemittel oder Lackbindemittelkomponenten beispielhaft erwähnt: in Wasser gelöste oder dispergierte, Hydroxylgruppen aufweisende Polyacrylate, insbesondere solche des Molekulargewichtsbereichs 1.000 bis 20.000, die mit organischen Polyisocyanaten als Vernetzer wertvolle Zweikomponenten-Bindemittel darstellen oder in Wasser dispergierte, gegebenenfalls Urethan-modifizierte, Hydroxylgruppen aufweisende Polyesterharze der aus der Polyester- und Alkydharzchemie bekannten Art. Prinzipiell sind als Reaktionspartner für die erfindungsgemäßen Polyisocyanatgemische alle in Wasser gelösten oder dispergierten Bindemittel, die gegenüber Isocyanaten reaktive Gruppen aufweisen, geeignet. Hierzu zählen beispielsweise auch
in Wasser dispergierte Polyurethane oder Polyhamstoffe, die aufgrund der in den Urethan- bzw. Hamstoffgruppen vorliegenden aktiven Wasserstoffatome mit Polyisocyanaten vemetzbar sind.In this context, examples of paint binders or paint binder components that may be mentioned are: polyacrylates containing hydroxyl groups, dissolved or dispersed in water, in particular those with a molecular weight in the range from 1,000 to 20,000, which, with organic polyisocyanates as crosslinkers, represent valuable two-component binders, or dispersed in water, optionally urethane-modified, Polyester resins containing hydroxyl groups of the type known from polyester and alkyd resin chemistry. Suitable reactants for the polyisocyanate mixtures according to the invention are in principle all binders which are dissolved or dispersed in water and contain isocyanate-reactive groups. This also includes, for example polyurethanes or polyureas dispersed in water which can be crosslinked with polyisocyanates because of the active hydrogen atoms present in the urethane or urea groups.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Beschichtungsmittel enthaltend mindestens ein erfmdungsgemäßes hydrophiles Uretdionstrukturen enthaltendes Polyisocyanat.Another subject of the present invention is a coating composition containing at least one polyisocyanate according to the invention containing hydrophilic uretdione structures.
Bei der erfmdungsgemäßen Verwendung als Vemetzerkomponente für wäßrige Lackbindemittel werden die erfmdungsgemäßen hydrophilen Polyisocyanate im allgemeinen in solchen Mengen eingesetzt, die einem Äquivalentverhältnis von NCO-Gruppen zu gegenüber NCO-Gruppen reaktionsfähigen Gruppen, insbesondere alkoholischen Hydroxylgruppen, von 0,5: 1 bis 2: 1 entsprechen. When used according to the invention as a crosslinking component for aqueous paint binders, the hydrophilic polyisocyanates according to the invention are generally used in amounts corresponding to an equivalent ratio of NCO groups to NCO-reactive groups, in particular alcoholic hydroxyl groups, of 0.5:1 to 2:1 correspond to.
Gegebenenfalls können die erfindungsgemäßen hydrophilen Polyisocyanate in untergeordneten Mengen auch nichtfünktionellen wäßrigen Lackbindemitteln zur Erzielung ganz spezieller Eigenschaften, beispielsweise als Additiv zur Haftverbesserung zugemischt werden. If appropriate, the hydrophilic polyisocyanates according to the invention can also be admixed in minor amounts to non-functional aqueous paint binders in order to achieve very specific properties, for example as an additive to improve adhesion.
Selbstverständlich können die erfindungsgemäßen hydrophilen Polyisocyanate auch in mit aus der Polyurethanchemie an sich bekannten Blockierungsmitteln blockierter Form in Kombination mit den obengenannten wäßrigen Lackbindemitteln oder Lackbindemittelkomponenten im Sinne von wäßrigen Einkomponenten-PUR-Einbrennsystemen eingesetzt werden. Geeignete Blockierungsmittel sind beispielsweise Malonsäurediethylester, Acetessigester, Acetonoxim, Butanonoxim, s- Caprolactam, 3,5-Dimethylpyrazol, 1,2,4-Triazol, Dimethyl- 1, 2, 4-triazol, Imidazol oder beliebige Gemische dieser Blockierungsmittel. Of course, the hydrophilic polyisocyanates according to the invention can also be used in a form blocked with blocking agents known per se from polyurethane chemistry in combination with the abovementioned aqueous paint binders or paint binder components in the sense of aqueous one-component PUR stoving systems. Examples of suitable blocking agents are diethyl malonate, acetoacetic ester, acetone oxime, butanone oxime, s-caprolactam, 3,5-dimethylpyrazole, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole or any mixture of these blocking agents.
Als Untergründe für die mit Hilfe der erfindungsgemäßen hydrophilen Polyisocyanate formulierten wäßrigen Beschichtungen kommen beliebige Substrate in Betracht, wie z. B. Metall, Holz, Glas, Stein, keramische Materialien, Beton, harte und flexible Kunststoffe, Textilien, Leder und Papier, die vor der Beschichtung gegebenenfalls auch mit üblichen Grundierungen versehen werden können.Any desired substrates can be used as substrates for the aqueous coatings formulated with the aid of the hydrophilic polyisocyanates according to the invention, such as, for example, B. metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textiles, leather and paper, which can optionally also be provided with conventional primers before coating.
Im Allgemeinen besitzen die mit den erfindungsgemäßen hydrophilen Polyisocyanaten formulierten wäßrigen Beschichtungsmittel, denen gegebenenfalls die auf dem Lacksektor üblichen Hilfs- und Zusatzmittel, wie z. B. Verlaufshilfsmittel, Farbpigmente, Füllstoffe, Mattierungsmittel oder Emulgatoren, einverleibt werden können, schon bei Raumtemperaturtrocknung gute lacktechnische Eigenschaften. In general, the aqueous coating compositions formulated with the hydrophilic polyisocyanates according to the invention and to which the auxiliaries and additives customary in the coatings sector, such as e.g. B. leveling agents, color pigments, fillers, matting agents or emulsifiers can be incorporated, good paint properties even at room temperature drying.
Selbstverständlich lassen sie sich jedoch auch unter forcierten Bedingungen bei erhöhter Temperatur bzw. durch Einbrennen bei Temperaturen bis 260 °C trocknen. Of course, they can also be dried under forced conditions at elevated temperatures or by baking at temperatures of up to 260 °C.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Substrat, beschichtet mit einem gegebenenfalls unter Wärmeeinwirkung ausgehärteten erfindungsgemäßen Beschichtungsmittel.A further subject matter of the present invention is a substrate coated with a coating composition according to the invention, optionally cured under the action of heat.
Aufgrund ihrer hervorragenden Wasseremulgierbarkeit, die eine homogene, besonders feinteilige Verteilung in wäßrigen Lackbindemitteln ermöglicht, führt die Verwendung der erfmdungsgemäßen
hydrophilen Polyisocyanate als Vemetzerkomponente für wäßrige Polyurethanlacke zu Beschichtungen mit hervorragenden optischen Eigenschaften, insbesondere hohem Oberflächenglanz, Verlauf und hoher Transparenz. Due to their excellent water-emulsifiability, which allows a homogeneous, particularly finely divided distribution in aqueous paint binders, the use of the inventive leads hydrophilic polyisocyanates as a crosslinking component for aqueous polyurethane coatings to give coatings with excellent optical properties, in particular high surface gloss, leveling and high transparency.
Neben der bevorzugten Verwendung als Vemetzerkomponenten für wäßrige 2K-PUR-Lacke eignen sich die erfmdungsgemäßen hydrophilen Polyisocyanate hervorragend als Vernetzer für wäßrige Dispersionsklebstoffe, Leder- und Textilbeschichtungen oder Textildruckpasten, als Papierhilfsmittel, die frei von Adsorbierbaren Organisch gebundenen Halogenen (AOX) sind, oder auch als Zusatzmittel für mineralische Baustoffe, beispielsweise Beton- oder Mörtelmassen. In addition to the preferred use as crosslinking components for aqueous 2K PUR coatings, the hydrophilic polyisocyanates according to the invention are outstandingly suitable as crosslinking agents for aqueous dispersion adhesives, leather and textile coatings or textile printing pastes, as paper auxiliaries that are free from adsorbable organically bound halogens (AOX), or else as an additive for mineral building materials, for example concrete or mortar masses.
Die für das erfmdungsgemäße Verfahren als bevorzugt gekennzeichneten Merkmale sind auch für die weiteren Erfmdungsgegenstände bevorzugt. The features marked as preferred for the method according to the invention are also preferred for the further objects of the invention.
Die nachfolgenden Beispiele dienen zur Verdeutlichung der vorliegenden Erfindung, sollen aber keinesfalls als Einschränkung des Schutzbereichs verstanden werden.
The following examples serve to illustrate the present invention, but should in no way be understood as limiting the scope of protection.
Beispiele examples
Alle Prozentangaben beziehen sich, soweit nichts Anderslautendes vermerkt, auf das Gewicht.All percentages are by weight unless otherwise noted.
Die Bestimmung der NCO-Gehalte erfolgte titrimetrisch nach DIN EN ISO 11909:2007-05. The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.
Sämtliche Viskositätsmessungen erfolgten mit einem Physica MCR 51 Rheometer der Fa. Anton Paar Germany GmbH (DE) nach DIN EN ISO 3219: 1994-10 bei einer Scherrate von 250 s-1.All viscosity measurements were carried out using a Physica MCR 51 rheometer from Anton Paar Germany GmbH (DE) in accordance with DIN EN ISO 3219: 1994-10 at a shear rate of 250 s-1.
Die Restmonomerengehalte wurden nach DIN EN ISO 10283:2007-11 gaschromatographisch mit internem Standard gemessen. The residual monomer content was measured according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard.
Die Messung der Platin-Cobalt-Farbzahl erfolgte spektrofotometrisch nach DIN EN ISO 6271- 2:2005-03 mit einem LICO 400-Spektrofotometer der Fa. Lange, DE. The platinum-cobalt color number was measured spectrophotometrically in accordance with DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, DE.
Die Gehalte (mol-%) der in den Polyisocyanaten A) vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen wurden aus den Integralen protonenentkoppelter 13C-NMR-Spektren (aufgenommen an einem Gerät Bruker DPX-400) errechnet und beziehen sich jeweils auf die Summe an vorliegenden Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen. Die Gehalte (mol-%) an gegebenenfalls in den Polyisocyanaten A) vorliegenden Uretonimistrukturen wurden ebenfalls aus den Integralen der protonenentkoppelten 13C-NMR-Spektren errechnet und beziehen sich auf Uretdionstrukturen. Im Falle von in CDCE gelösten HDI-Polyisocyanaten weisen die einzelnen Strukturelemente folgende chemische Verschiebungen (in ppm) auf: Uretdion: 157.1; Isocyanurat: 148.4; Iminooxadiazindion: 147.8, 144.3 und 135.3; Allophanat: 155.7 und 153.8, Biuret: 155,5; Urethan: 156,3; Oxadiazintrion: 147,8 und 143,9; Uretonimin: 158,7 und 144,6. The contents (mol %) of the uretdione, optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanates A) were determined from the integrals of proton-decoupled 13 C-NMR spectra (recorded on a Bruker DPX-400 device) and relate in each case to the sum of the uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures present. The contents (mol %) of any uretonime structures present in the polyisocyanates A) were also calculated from the integrals of the proton-decoupled 13 C-NMR spectra and relate to uretdione structures. In the case of HDI polyisocyanates dissolved in CDCE, the individual structural elements have the following chemical shifts (in ppm): uretdione: 157.1; Isocyanurate: 148.4; iminooxadiazinedione: 147.8, 144.3 and 135.3; allophanate: 155.7 and 153.8, biuret: 155.5; urethane: 156.3; oxadiazinetrione: 147.8 and 143.9; Uretonimine: 158.7 and 144.6.
Die Phosphorgehalte in den Ausgangspolyisocyanaten A) und nichtionisch hydrophilen organischen Verbindungen B) wurden durch induktiv gekoppelte Plasma-Atom-Emissionsspektrometrie (ICP- OES) nach DIN EN ISO 11885:2009-09 nach Mikrowellenaufschluss bestimmt. Die Nachweisgrenze liegt bei diesem Verfahren bei <1 ppm.
The phosphorus contents in the starting polyisocyanates A) and nonionic hydrophilic organic compounds B) were determined by inductively coupled plasma atomic emission spectrometry (ICP-OES) to DIN EN ISO 11885:2009-09 after microwave digestion. The detection limit for this method is <1 ppm.
Ausgangsverbindungen output connections
Polyisocyanate A) Polyisocyanates A)
Ausgangspolyisocyanat Al) starting polyisocyanate Al)
Polyisocyanat, hergestellt durch katalytische Trimerisierung von HDI in Anlehnung an Beispiel 11 der EP-A 330 966, mit der Änderung, dass die Reaktion bei einem NCO-Gehalt der Rohmischung von 40 % durch Zugabe von Dibutylphosphat gestoppt wurde. Anschließend wurde nicht umgesetztes HDI durch Dünnschichtdestillation bei einer Temperatur von 130°C und einem Druck von 0,2 mbar abgetrennt. Polyisocyanate produced by catalytic trimerization of HDI based on Example 11 of EP-A 330 966, with the change that the reaction was stopped at an NCO content of the raw mixture of 40% by adding dibutyl phosphate. Subsequently, unreacted HDI was removed by thin-layer distillation at a temperature of 130° C. and a pressure of 0.2 mbar.
Das Produkt wies folgende Kenndaten und Zusammensetzung auf: The product had the following characteristics and composition:
NCO-Gehalt: 21,7 % monomeres HDI: 0,06 % NCO content: 21.7% monomeric HDI: 0.06%
Viskosität (23°C): 3080 mPas Viscosity (23°C): 3080 mPas
Farbzahl (Hazen): 8 Color number (Hazen): 8
Phosphorgehalt: 8 ppm Phosphorus content: 8 ppm
Uretdionstrukturen: 0,9 mol-% Uretdione structures: 0.9 mol%
Isocyanmatstrukturen: 90,1 mol-% Isocyanate structures: 90.1 mol%
Iminooxadazindionstrukturen: 3,6 mol-% Iminooxadazinedione structures: 3.6 mol%
Allophanatstrukturen: 5,4 mol-% Allophanate structures: 5.4 mol%
Uretoniminstrukturen: nicht nachweisbar Uretonimine structures: not detectable
Ausgangspolyisocyanat A2) starting polyisocyanate A2)
Polyisocyanat, hergestellt in Anlehnung an Vergleichsbeispiel 2a der WO 2018/153801, durch Trimeriserung von HDI unter Verwendung einer 20 %-igen Lösung von 5-Azonia- spiro[4.5]decaniumhydrogendifluorid in 2-Ethylhexanol als Katalysator, Reaktionsstoppung bei einem NCO-Gehalt der Rohmischung von 44,8 % durch Zugabe einer zur Katalysatormenge äquivalenten Menge einer 70 %igen Lösung von Dodecylbenzolsulfonsäure in Isopropanol und anschließende Abtrennung des nicht umgesetzten HDI durch Dünnschichtdestillation bei einer Temperatur von 130°C und einem Druck von 0,2 mbar. Polyisocyanate, prepared based on Comparative Example 2a of WO 2018/153801, by trimerization of HDI using a 20% solution of 5-azoniaspiro[4.5]decanium hydrogen difluoride in 2-ethylhexanol as a catalyst, stopping the reaction at an NCO content of Crude mixture of 44.8% by adding an amount of a 70% solution of dodecylbenzenesulfonic acid in isopropanol equivalent to the amount of catalyst and subsequent removal of the unreacted HDI by thin-layer distillation at a temperature of 130° C. and a pressure of 0.2 mbar.
Das Produkt wies folgende Kenndaten und Zusammensetzung auf: The product had the following characteristics and composition:
NCO-Gehalt: 23,5 % monomeres HDI: 0,11 % NCO content: 23.5% monomeric HDI: 0.11%
Viskosität (23°C): 720 mPas
Farbzahl (Hazen): 49 Viscosity (23°C): 720 mPas Color number (Hazen): 49
Phosphorgehalt: < 1 ppm Phosphorus content: < 1 ppm
Uretdionstrukturen: 4,9 mol-% Uretdione structures: 4.9 mol%
Isocyanuratstrukturen: 46,7 mol-% Isocyanurate structures: 46.7 mol%
Iminooxadazindionstrukturen: 48,4 mol-% Iminooxadazinedione structures: 48.4 mol%
Uretoniminstrukturen: nicht nachweisbar Uretonimine structures: not detectable
Ausgangspolyisocyanat A3) starting polyisocyanate A3)
Polyisocyanat, hergestellt durch thermische Dimerisierung und anschließende Hexamethyldisilazan- katalysierte Trimerisierung von HDI nach Beispiel 4 der US 2004/0106762. Polyisocyanate produced by thermal dimerization and subsequent hexamethyldisilazane-catalyzed trimerization of HDI according to example 4 of US 2004/0106762.
Das Produkt wies folgende Kenndaten und Zusammensetzung auf: The product had the following characteristics and composition:
NCO-Gehalt: 23,1 % monomeres HDI: 0,10 % NCO content: 23.1% monomeric HDI: 0.10%
Viskosität (23°C): 710 mPas Viscosity (23°C): 710 mPas
Farbzahl (Hazen): 8 Color number (Hazen): 8
Phosphorgehalt: < 1 ppm Phosphorus content: < 1 ppm
Uretdionstrukturen: 19,9 mol-% Uretdione structures: 19.9 mol%
Isocyanuratstrukturen : 69,7 mol-% Isocyanurate structures: 69.7 mol%
Urethanstrukturen: 10,4 mol-% Urethane structures: 10.4 mol%
Uretoniminstrukturen: 0,15 mol-% (bezogen auf Uretdionstrukturen) Uretonimine structures: 0.15 mol% (based on uretdione structures)
Ausgangspolyisocyanat A4) starting polyisocyanate A4)
Polyisocyanat, hergestellt nach Beispiel 11 der EP-A 330 966, mit der Änderung, dass als Katalysatorlösemittel 2-Ethylhexanol statt 2-Ethyl-l,3-hexandiol eingesetzt wurde und die Reaktion bei einem NCO-Gehalt der Rohmischung von 42,5 % durch Zugabe von Dibutylphosphat gestoppt wurde. Anschließend wurde nicht umgesetztes HDI durch Dünnschichtdestillation bei einer Temperatur von 130°C und einem Druck von 0,2 mbar abgetrennt. Polyisocyanate prepared according to Example 11 of EP-A 330 966, with the change that 2-ethylhexanol was used as the catalyst solvent instead of 2-ethyl-1,3-hexanediol and the reaction was carried out at an NCO content of the raw mixture of 42.5% was stopped by adding dibutyl phosphate. Subsequently, unreacted HDI was removed by thin-layer distillation at a temperature of 130° C. and a pressure of 0.2 mbar.
Das Produkt wies folgende Kenndaten und Zusammensetzung auf: The product had the following characteristics and composition:
NCO-Gehalt: 22,9 % monomeres HDI: 0,08 % NCO content: 22.9% monomeric HDI: 0.08%
Viskosität (23°C): 1210 mPas Viscosity (23°C): 1210 mPas
Farbzahl (Hazen): 10
Phosphorgehalt: 14 ppm Color number (Hazen): 10 Phosphorus content: 14 ppm
Uretdionstrukturen: 1,9 mol-% Uretdione structures: 1.9 mol%
Isocyanuratstrukturen: 89,0 mol-% Isocyanurate structures: 89.0 mol%
Iminooxadazindionstrukturen: 4,3 mol-% Iminooxadazinedione structures: 4.3 mol%
Allophanatstrukturen: 4,8 mol-% Allophanate structures: 4.8 mol%
Uretoniminstrukturen: nicht nachweisbar Uretonimine structures: not detectable
Nichtionisch hydrophile organische Verbindung B) Nonionic hydrophilic organic compound B)
Bl) Methoxypolyethylenglykol MPEG 350, Bl) methoxypolyethylene glycol MPEG 350,
OH-Zahl: 160 mg KOH/g, Äquivalentgewicht: 351 g/mol pH-Wert: 6,3 OH number: 160 mg KOH/g, equivalent weight: 351 g/mol pH value: 6.3
Phosphorgehalt: < 1 ppm Phosphorus content: < 1 ppm
B2) Methoxypolyethylenglykol MPEG 350, B2) methoxypolyethylene glycol MPEG 350,
OH-Zahl: 162 mg KOH/g, Äquivalentgewicht: 346 g/mol pH-Wert: 3,7 OH number: 162 mg KOH/g, equivalent weight: 346 g/mol pH value: 3.7
Phosphorgehalt: 120 ppm Phosphorus content: 120 ppm
B3) Methoxypolyethylenglykol MPEG 500, B3) methoxypolyethylene glycol MPEG 500,
OH-Zahl: 112 mg KOH/g, Äquivalentgewicht: 501 g/mol pH-Wert: 4,9 OH number: 112 mg KOH/g, equivalent weight: 501 g/mol pH value: 4.9
Phosphorgehalt: < 1 ppm Phosphorus content: < 1 ppm
B4) Methoxypolyethylenglykol MPEG 500, B4) methoxypolyethylene glycol MPEG 500,
OH-Zahl: 111 mg KOH/g, Äquivalentgewicht: 505 g/mol pH-Wert: 3,9 OH number: 111 mg KOH/g, equivalent weight: 505 g/mol pH value: 3.9
Phosphorgehalt: 110 ppm Phosphorus content: 110 ppm
Beispiel 1 (erfindungsgemäß) Example 1 (according to the invention)
870 g (4,50 val) der Polyisocyanatkomponente Al) wurden bei 100 °C unter trockenem Stickstoff und Rühren vorgelegt, innerhalb von 30 min mit 130 g (0,37 val) der nichtionisch hydrophilen organischen Verbindung Bl) versetzt und bei dieser Temperatur weiter gerührt, bis der NCO-Gehalt der Mischung nach etwa 2 h auf den einer vollständigen Urethanisierung entsprechenden Wert gefallen war. Nach Abkühlen auf Raumtemperatur lag ein farbloses, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten vor: 870 g (4.50 eq) of the polyisocyanate component A1) were initially charged at 100° C. under dry nitrogen and stirred, 130 g (0.37 eq) of the nonionic hydrophilic organic compound B1) were added within 30 minutes and the mixture continued at this temperature stirred until the NCO content of the mixture had fallen after about 2 h to the value corresponding to complete urethanization. After cooling to room temperature, a colourless, completely clear, hydrophilically modified polyisocyanate was obtained with the following characteristics:
NCO-Gehalt: 17,2 % monomeres HDI: 0,05 %
Viskosität (23 °C): 3410 mPas NCO content: 17.2% monomeric HDI: 0.05% Viscosity (23°C): 3410 mPas
Farbzahl (Hazen): 10 Color number (Hazen): 10
P-Gehalt (berechnet): 7 ppm P content (calculated): 7 ppm
Beispiel 2 (erfmdungsgemäß) Example 2 (according to the invention)
Beispiel 1 wurde wiederholt, wobei der Polyisocyanatkomponente Al) vor Beginn der Zugabe der nichtionisch hydrophilen organischen Verbindung Bl) 0,5 g (50 ppm bezogen auf Gesamtansatz) Dibutylphosphat als Stabilisator zugesetzt wurden. Es wurde ein farbloses, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten erhalten: Example 1 was repeated, with 0.5 g (50 ppm based on the total batch) of dibutyl phosphate being added as a stabilizer to the polyisocyanate component A1) before the start of the addition of the nonionic hydrophilic organic compound B1). A colorless, completely clear, hydrophilically modified polyisocyanate with the following characteristics was obtained:
NCO-Gehalt: 17,3 % monomeres HDI: 0,07 % NCO content: 17.3% monomeric HDI: 0.07%
Viskosität (23 °C): 3290 mPas Viscosity (23 °C): 3290 mPas
Farbzahl (Hazen): 10 Color number (Hazen): 10
P-Gehalt (berechnet): 14,3 ppm P content (calculated): 14.3 ppm
Beispiel 3 (Vergleich) Example 3 (comparison)
Nach dem in Beispiel 1 beschriebenen Verfahren wurden 870 g (4,50 val) der Polyisocyanatkomponente Al) mit 130 g (0,38 val) der nichtionisch hydrophilen organischen Verbindung B2) umgesetzt. Man erhielt ein farbloses, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten: Using the process described in Example 1, 870 g (4.50 equivalents) of the polyisocyanate component A1) were reacted with 130 g (0.38 equivalents) of the nonionic hydrophilic organic compound B2). A colorless, completely clear, hydrophilically modified polyisocyanate with the following characteristics was obtained:
NCO-Gehalt: 17,3 % monomeres HDI: 0,12 % NCO content: 17.3% monomeric HDI: 0.12%
Viskosität (23 °C): 3200 mPas Viscosity (23°C): 3200 mPas
Farbzahl (Hazen): 9 Color number (Hazen): 9
P-Gehalt (berechnet): 22,6 ppm P content (calculated): 22.6 ppm
Beispiel 4 (erfindungsgemäß) Example 4 (according to the invention)
830 g (4,64 val) der Polyisocyanatkomponente A2) wurden bei 100 °C unter trockenem Stickstoff und Rühren vorgelegt, innerhalb von 30 min mit 170 g (0,48 val) der nichtionisch hydrophilen organischen Verbindung Bl) versetzt und bei dieser Temperatur weiter gerührt, bis der NCO-Gehalt der Mischung nach etwa 2 h auf den einer vollständigen Urethanisierung entsprechenden Wert gefallen war. Nach Abkühlen auf Raumtemperatur lag ein leicht gelbes, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten vor:
NCO-Gehalt: 17,5 % monomeres HDI: 0,09 % 830 g (4.64 eq) of the polyisocyanate component A2) were initially charged at 100° C. under dry nitrogen and stirred, 170 g (0.48 eq) of the nonionic hydrophilic organic compound B1) were added within 30 minutes and the mixture continued at this temperature stirred until the NCO content of the mixture had fallen after about 2 h to the value corresponding to complete urethanization. After cooling to room temperature, a slightly yellow, completely clear, hydrophilically modified polyisocyanate was obtained with the following characteristics: NCO content: 17.5% monomeric HDI: 0.09%
Viskosität (23 °C): 815 mPas Viscosity (23°C): 815 mPas
Farbzahl (Hazen): 37 Color number (Hazen): 37
P-Gehalt (berechnet):
1 ppm P content (calculated): 1 ppm
Beispiel 5 (Vergleich) Example 5 (comparison)
Nach dem in Beispiel 3 beschriebenen Verfahren wurden 830 g (4,64 val) der Polyisocyanatkomponente A2) mit 170 g (0,48 val) der nichtionisch hydrophilen organischen Verbindung B2) umgesetzt. Man erhielt ein leicht gelbes, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten: Using the process described in Example 3, 830 g (4.64 equivalents) of the polyisocyanate component A2) were reacted with 170 g (0.48 equivalents) of the nonionic hydrophilic organic compound B2). A slightly yellow, completely clear, hydrophilically modified polyisocyanate with the following characteristics was obtained:
NCO-Gehalt: 17,5 % monomeres HDI: 0,13 % NCO content: 17.5% monomeric HDI: 0.13%
Viskosität (23 °C): 810 mPas Viscosity (23 °C): 810 mPas
Farbzahl (Hazen): 34 Color number (Hazen): 34
P-Gehalt (berechnet): 20,4 ppm P content (calculated): 20.4 ppm
Beispiel 6 (erfmdungsgemäß) Example 6 (according to the invention)
800 g (4,40 val) der Polyisocyanatkomponente A3) wurden bei 80 °C unter trockenem Stickstoff und Rühren vorgelegt, innerhalb von 30 min mit 200 g (0,40 val) der nichtionisch hydrophilen organischen Verbindung B3) versetzt und bei dieser Temperatur weiter gerührt, bis der NCO-Gehalt der Mischung nach etwa 3,5 h auf den einer vollständigen Urethanisierung entsprechenden Wert gefallen war. Nach Abkühlen auf Raumtemperatur lag ein leicht gelbes, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten vor: 800 g (4.40 eq) of polyisocyanate component A3) were initially charged at 80° C. under dry nitrogen and stirred, 200 g (0.40 eq) of nonionic hydrophilic organic compound B3) were added within 30 minutes and further at this temperature stirred until the NCO content of the mixture had fallen after about 3.5 hours to the value corresponding to complete urethanization. After cooling to room temperature, a slightly yellow, completely clear, hydrophilically modified polyisocyanate was obtained with the following characteristics:
NCO-Gehalt: 16,8 % monomeres HDI: 0,07 % NCO content: 16.8% monomeric HDI: 0.07%
Viskosität (23 °C): 835 mPas Viscosity (23°C): 835 mPas
Farbzahl (Hazen): 7 Color number (Hazen): 7
P-Gehalt (berechnet):
Beispiel 7 (Vergleich) P content (calculated): Example 7 (comparison)
Nach dem in Beispiel 5 beschriebenen Verfahren wurden 800 g (4,13 val) der Polyisocyanatkomponente A3) mit 200 g (0,40 val) der nichtionisch hydrophilen organischen Verbindung B4) umgesetzt. Man erhielt ein farbloses, völlig klares, hydrophil modifiziertes Polyisocyanat mit folgenden Kenndaten: Using the process described in Example 5, 800 g (4.13 equivalents) of the polyisocyanate component A3) were reacted with 200 g (0.40 equivalents) of the nonionic hydrophilic organic compound B4). A colorless, completely clear, hydrophilically modified polyisocyanate with the following characteristics was obtained:
NCO-Gehalt: 15,7 % monomeres HDI: 0,13 % NCO content: 15.7% monomeric HDI: 0.13%
Viskosität (23 °C): 260 mPas Viscosity (23°C): 260 mPas
Farbzahl (Hazen): 8 Color number (Hazen): 8
P-Gehalt (berechnet): 22,0 ppm P content (calculated): 22.0 ppm
Die Beispiele 1, 2, 4 und 6 belegen, dass die Umsetzung der Ausgangspolyisocyanate Al), A2) und A3), die Uretdionstrukturen und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten, mit phosphorfreien Polyetheralkoholen bei 100°C nichtionisch hydrophilierte Polyisocyanate liefert, die Monomergehalte von unter 0,10 % aufweisen. Dagegen zeigen die Vergleichsbeispielen 3, 5 und 7, dass die Umsetzung derselben Ausgangspolyisocyanate Al), A2) und A3) mit Polyetheralkoholen, die mehr als 50 ppm Phosphor enthalten, zu hydrophil modifizierten Polyisocyanaten mit Monomergehalten von über 0,10 % fuhrt, wenn gleichzeitig die Summe an Phosphor im jeweiligen Ausgangspolyisocyanat und Polyetheralkohol mehr als 20 ppm beträgt. Examples 1, 2, 4 and 6 demonstrate that the reaction of the starting polyisocyanates A1), A2) and A3) containing uretdione structures and less than 0.20 mol % of uretonimine structures based on the uretdione structures with phosphorus-free polyether alcohols at 100° C provides nonionically hydrophilized polyisocyanates which have a monomer content of less than 0.10%. In contrast, Comparative Examples 3, 5 and 7 show that the reaction of the same starting polyisocyanates A1), A2) and A3) with polyether alcohols containing more than 50 ppm phosphorus leads to hydrophilically modified polyisocyanates with monomer contents of more than 0.10%, if simultaneously the sum of phosphorus in the respective starting polyisocyanate and polyether alcohol is more than 20 ppm.
Beispiele 8 bis 13 (erfindungsgemäß und Vergleich) Examples 8 to 13 (according to the invention and comparison)
Nach dem in Beispiel 1 beschriebenen Verfahren wurden die Polyisocyanatkomponente Al) bzw. A4) jeweils mit aus Gemischen der Polyetheralkohole Bl) und B2) bestehenden nichtionisch hydrophilen organischen Verbindungen, die unterschiedliche Mengen an Phosphor enthielten umgesetzt. Die nachfolgende Tabelle zeigt die jeweiligen Zusammensetzungen der Reaktionsgemische, Gesamt-Phosphorgehalte von Polyether- und Polyisocyanatkomponente sowie die Kenndaten der erhaltenen Reaktionsprodukte.
Using the process described in Example 1, the polyisocyanate components A1) and A4) were each reacted with nonionic hydrophilic organic compounds consisting of mixtures of the polyether alcohols B1) and B2) and containing different amounts of phosphorus. The table below shows the respective compositions of the reaction mixtures, the total phosphorus content of the polyether and polyisocyanate components and the characteristics of the reaction products obtained.
inklusive P aus Dibutylphosphat (Stabilisator)
including P from dibutyl phosphate (stabilizer)
Die erfindungsgemäßen Beispiele 8, 10 und 12 zeigen, dass die Umsetzung der Ausgangspolyisocyanate Al) und A4), die Uretdionstrukturen und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten, mit Polyetheralkoholen deren Phosphorgehalt höchstens 50 ppm beträgt, bei 100 °C nichtionisch hydrophilierte Polyisocyanate mit Monomergehalten von unter 0,10 % ergibt, wenn ihr Gesamtgehalt an Phosphor höchstens 20 ppm beträgt. Examples 8, 10 and 12 according to the invention show that the reaction of the starting polyisocyanates A1) and A4) containing uretdione structures and less than 0.20 mol % of uretonimine structures, based on the uretdione structures, with polyether alcohols whose phosphorus content is at most 50 ppm 100 °C nonionically hydrophilized polyisocyanates with monomer contents of less than 0.10% if their total phosphorus content is not more than 20 ppm.
Die Vergleichsbeispiele 9, 11 und 13 lieferten dagegen ausgehend von denselben Polyisocyanatkomponenten in Kombination mit Polyetheralkoholgemischen, die mehr als 50 ppm Phosphor enthielten, bei Phosphor-Gesamtgehalten im Reaktionsgemisch von mehr als 20 ppm hydrophil modifizierte Polyisocyanaten mit Monomergehalten von jeweils mehr als 0,10 %.
In contrast, Comparative Examples 9, 11 and 13, starting from the same polyisocyanate components in combination with polyether alcohol mixtures which contained more than 50 ppm phosphorus, gave hydrophilically modified polyisocyanates with total phosphorus contents in the reaction mixture of more than 20 ppm and monomer contents of more than 0.10% in each case. .
Claims
1. Verfahren zur Herstellung hydrophil modifizierter Polyisocyanate mit einem Gehalt an monomeren Diisocyanaten von weniger als 0,10 Gew.-%, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, umfassend eine Umsetzung von 1. A process for the preparation of hydrophilically modified polyisocyanates containing less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, comprising a reaction of
A) mindestens einer Polyisocyanatkomponente mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen, die mindestens Uretdionstrukturen und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen aufweist, mit A) at least one polyisocyanate component with aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups, which has at least uretdione structures and less than 0.20 mol % of uretonimine structures, based on the uretdione structures
B) mindestens einer nichtionisch hydrophilen organischen Verbindung, die mindestens eine gegenüber Isocyanaten reaktive Gruppe aufweist, wobei die nichtionisch hydrophile organische Verbindung B) einen Gehalt an Phosphor von höchstens 50 ppm aufweist, und der Gesamtgehalt an Phosphor bezogen auf die Komponenten A) und B) des hydrophil modifizierten Polyisocyanats höchstens 20 ppm beträgt. B) at least one nonionic hydrophilic organic compound which has at least one isocyanate-reactive group, the nonionic hydrophilic organic compound B) having a phosphorus content of at most 50 ppm, and the total phosphorus content based on components A) and B) of the hydrophilically modified polyisocyanate is at most 20 ppm.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Polyisocyanatkomponente A) einen Gehalt an Uretdionstrukturen von mindestens 0,6 mol-%, vorzugsweise von 0,8 bis 25 mol-%, jeweils bezogen auf die Gesamtmenge aller im Polyisocyanat vorliegenden Uretdion-, gegebenenfalls Isocyanurat-, Iminooxadiazindion-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen aufweist, wobei die Gesamtmenge aller im Polyisocyanat vorliegenden Iminooxadiazindion-, Uretdion-, Isocyanurat-, Allophanat-, Biuret-, Urethan- und/oder Oxadiazintrionstrukturen 100 mol-% ergibt. 2. The method according to claim 1, characterized in that the polyisocyanate component A) has a content of uretdione structures of at least 0.6 mol%, preferably from 0.8 to 25 mol%, based in each case on the total amount of all uretdione present in the polyisocyanate , optionally isocyanurate, iminooxadiazinedione, allophanate, biuret, urethane and/or oxadiazinetrione structures, the total amount of all iminooxadiazinedione, uretdione, isocyanurate, allophanate, biuret, urethane and/or oxadiazinetrione structures present in the polyisocyanate 100 mol%.
3. Verfahren gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass die Polyisocyanatkomponente A) mindestens Uretdion- und Isocyanuratstrukturen enthält.3. The method according to any one of claims 1 and 2, characterized in that the polyisocyanate component A) contains at least uretdione and isocyanurate structures.
4. Verfahren gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass die Polyisocyanatkomponente A) ausschließlich aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen aufweist. 4. The method according to any one of claims 1 and 2, characterized in that the polyisocyanate component A) has exclusively aliphatically and / or cycloaliphatically bound isocyanate groups.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei der Polyisocyanatkomponente A) um eine auf Basis von PDI, HDI, IPDI und/oder 2,4‘- und 4,4'- Diisocyanatodicyclohexylmethan handelt. 5. The method according to any one of claims 1 to 4, characterized in that the polyisocyanate component A) is based on PDI, HDI, IPDI and/or 2,4'- and 4,4'-diisocyanatodicyclohexylmethane.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es sich bei der nichtionisch hydrophilen organischen Verbindung B) um ein- oder mehrwertige, im
statistischen Mittel 5 bis 50 Ethylenoxideinheiten pro Molekül aufweisende Polyalkylenoxid- polyetheralkohole handelt. 6. The method according to any one of claims 1 to 5, characterized in that the nonionic hydrophilic organic compound B) is mono- or polyvalent, im polyalkylene oxide polyether alcohols having a statistical average of 5 to 50 ethylene oxide units per molecule.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass es sich bei der nichtionisch hydrophilen organischen Verbindung B) um reine Polyethylenoxidpolyetheralkohole oder gemischte Polyalkylenoxidpolyetheralkohole handelt, deren Alkylenoxideinheiten zu mindestens 70 mol-% aus Ethylenoxideinheiten bestehen. 7. The process as claimed in claim 6, characterized in that the nonionic hydrophilic organic compound B) is pure polyethylene oxide polyether alcohols or mixed polyalkylene oxide polyether alcohols, the alkylene oxide units of which consist of at least 70 mol % ethylene oxide units.
8. Verfahren gemäß Anspruch 6 und 7, dadurch gekennzeichnet, dass die nichtionisch hydrophile organische Verbindung B) einen pH-Wert, gemessen an einer 5 %igen Lösung in Wasser, von 4,0 bis 8,0, vorzugsweise von 4,5 bis 7,5, besonders bevorzugt von 5,0 bis 7,0 aufweist.8. The method according to claim 6 and 7, characterized in that the nonionic hydrophilic organic compound B) has a pH, measured on a 5% solution in water, from 4.0 to 8.0, preferably from 4.5 to 7.5, more preferably from 5.0 to 7.0.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die nichtionisch hydrophilen Verbindungen B) in einer Menge von bis zu 30 Gew.-%, vorzugsweise von 2 bis 25 Gew.-%, besonders bevorzugt von 5 bis 20 Gew.-%, ganz besonders bevorzugt von 9 bis 17 Gew.-%, bezogen auf die Gesamtmenge der verwendeten Ausgangskomponenten A) und B) zum Einsatz kommen. 9. The method according to any one of claims 1 to 8, characterized in that the nonionic hydrophilic compounds B) are present in an amount of up to 30% by weight, preferably from 2 to 25% by weight, particularly preferably from 5 to 20% by weight %, very particularly preferably from 9 to 17% by weight, based on the total amount of starting components A) and B) used.
10. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die nichtionisch hydrophile organische Verbindung B) einen Gehalt an Phosphor von höchstens 40 ppm, vorzugsweise von höchstens 30 ppm, besonders bevorzugt keinen nachweisbaren Phosphor aufweist, wobei die Phosphorgehalte durch induktiv gekoppelte Plasma-Atom- Emissionsspektrometrie (ICP-OES) nach DIN EN ISO 11885:2009-09 nach Mikrowellenaufschluss bestimmt werden. 10. The method according to any one of claims 1 to 9, characterized in that the nonionic hydrophilic organic compound B) has a phosphorus content of at most 40 ppm, preferably at most 30 ppm, particularly preferably no detectable phosphorus, the phosphorus contents being inductively coupled Plasma atomic emission spectrometry (ICP-OES) according to DIN EN ISO 11885:2009-09 after microwave digestion.
11. Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Gesamtgehalt an Phosphor in dem aus den Komponenten A) und B) bestehenden hydrophil modifizierten Polyisocyanat von 3 bis 19 ppm, besonders bevorzugt von 5 bis 18 ppm beträgt. 11. The method according to any one of claims 1 to 10, characterized in that the total content of phosphorus in the hydrophilically modified polyisocyanate consisting of components A) and B) is from 3 to 19 ppm, particularly preferably from 5 to 18 ppm.
12. Nichtionisch hydrophil modifizierte Polyisocyanate, die Uretdionstrukturen und weniger als 0,20 mol-% an Uretoniminstrukturen bezogen auf die Uretdionstrukturen enthalten und weniger als 0,10 Gew.-% an monomeren Diisocyanaten, bezogen auf den Festkörpergehalt der hydrophil modifizierten Polyisocyanate, und höchstens 20 ppm an Phosphor aufweisen.12. Nonionically hydrophilically modified polyisocyanates containing uretdione structures and less than 0.20 mol% of uretonimine structures based on the uretdione structures and less than 0.10% by weight of monomeric diisocyanates, based on the solids content of the hydrophilically modified polyisocyanates, and at most Have 20 ppm of phosphorus.
13. Verwendung der nichtionisch hydrophil modifizierten Polyisocyanate gemäß Anspruch 12 als Ausgangskomponente bei der Herstellung von Polyurethankunststoffen. 13. Use of the nonionically hydrophilically modified polyisocyanates according to claim 12 as a starting component in the production of polyurethane plastics.
14. Beschichtungsmittel enthaltend nichtionisch hydrophil modifizierte Polyisocyanate gemäß Anspruch 12.
14. Coating compositions containing nonionically hydrophilically modified polyisocyanates as claimed in claim 12.
15. Substrat, beschichtet mit einem gegebenenfalls unter Wärmeeinwirkung ausgehärteten Beschichtungsmittel gemäß Anspruch 14.
15. A substrate coated with a coating composition according to claim 14, optionally cured under the action of heat.
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PCT/EP2021/085844 WO2022129140A1 (en) | 2020-12-15 | 2021-12-15 | Non-ionic hydrophilized polyisocyanates having a very low monomer content |
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DE2452532C3 (en) | 1974-11-06 | 1978-08-24 | Bayer Ag, 5090 Leverkusen | Process for the preparation of polyisocyanates with an isocyanurate structure |
DE2641380C2 (en) | 1976-09-15 | 1989-11-23 | Bayer Ag, 5090 Leverkusen | Process for the preparation of polyisocyanates with an isocyanurate structure |
DE3700209A1 (en) | 1987-01-07 | 1988-07-21 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES WITH BIURET STRUCTURE |
DE3806276A1 (en) | 1988-02-27 | 1989-09-07 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS AND THE USE THEREOF |
DE3811350A1 (en) | 1988-04-02 | 1989-10-19 | Bayer Ag | METHOD FOR THE PRODUCTION OF ISOCYANURATE POLYISOCYANATES, THE COMPOUNDS OBTAINED BY THIS PROCESS AND THEIR USE |
DE3814167A1 (en) | 1988-04-27 | 1989-11-09 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS AND THE USE THEREOF |
DE3900053A1 (en) | 1989-01-03 | 1990-07-12 | Bayer Ag | PROCESS FOR THE PREPARATION OF POLYISOCYANATES USING URETDION AND ISOCYANATE GROUPS, THE POLYISOCYANATES AVAILABLE FOR THIS PROCESS, AND THEIR USE IN TWO-COMPONENT POLYURETHANE VARNISHES |
DE3928503A1 (en) | 1989-08-29 | 1991-03-07 | Bayer Ag | METHOD FOR PRODUCING SOLUTIONS OF POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS IN LACQUER SOLVENTS AND THE USE THEREOF |
DE4136618A1 (en) * | 1991-11-07 | 1993-05-13 | Bayer Ag | Water-dispersible polyisocyanate mixtures |
DE19611849A1 (en) | 1996-03-26 | 1997-10-02 | Bayer Ag | New isocyanate trimer and isocyanate trimer mixtures, their production and use |
DE19654429A1 (en) * | 1996-12-24 | 1998-06-25 | Bayer Ag | Water-dispersible polyisocyanate mixtures as additives for concrete |
AU757808B2 (en) | 1997-08-12 | 2003-03-06 | Rhodia Chimie | Method for preparing (poly)isocyanate composition with reduced viscosity |
ES2209274T3 (en) | 1998-05-22 | 2004-06-16 | Bayer Aktiengesellschaft | MIXED POLYISOCIANATE MODIFIED THROUGH AVAILABLE POLYETERS. |
EP0962455B1 (en) | 1998-06-02 | 2002-11-06 | Bayer Aktiengesellschaft | Process for the preparation of imino-oxadiazine-dione groups containing polyisocyanates |
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 |
ES2618501T3 (en) | 2011-11-29 | 2017-06-21 | Covestro Deutschland Ag | Procedure for the preparation of polyisocyanates and their use |
HUE035077T2 (en) | 2013-12-10 | 2018-05-02 | Covestro Deutschland Ag | Polyisocyanates containing iminooxadiazine dione groups |
KR102327859B1 (en) | 2014-02-18 | 2021-11-17 | 코베스트로 도이칠란트 아게 | Process for isocyanate modification using spirocyclic ammonium salts as catalyst |
WO2015124503A1 (en) | 2014-02-18 | 2015-08-27 | Bayer Materialscience Ag | Method for isocyanate modification using catalysts with an npn sequence |
WO2016146474A1 (en) * | 2015-03-17 | 2016-09-22 | Covestro Deutschland Ag | Silane groups containing polyisocyanates based on 1,5-diisocyanatopentane |
EP3337836B1 (en) | 2015-08-17 | 2019-07-31 | Covestro Deutschland AG | Method for modifying of isocyanates using cyclic ammonium salts as catalyst |
JP6568996B2 (en) | 2016-03-09 | 2019-08-28 | 旭化成株式会社 | Polyisocyanate composition, coating composition, water-based coating composition, and coating substrate |
WO2018153801A1 (en) | 2017-02-22 | 2018-08-30 | Covestro Deutschland Ag | Method for modifying at least pentamethylene diisocyanate by means of spirocyclic ammonium salts as catalyst |
EP3543270A1 (en) * | 2018-03-23 | 2019-09-25 | Covestro Deutschland AG | Catalyst system for uretdion dispersions |
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