CN114316211A - Modified polyisocyanates - Google Patents
Modified polyisocyanates Download PDFInfo
- Publication number
- CN114316211A CN114316211A CN202011069929.1A CN202011069929A CN114316211A CN 114316211 A CN114316211 A CN 114316211A CN 202011069929 A CN202011069929 A CN 202011069929A CN 114316211 A CN114316211 A CN 114316211A
- Authority
- CN
- China
- Prior art keywords
- modified polyisocyanate
- weight
- polyisocyanate
- modified
- mol
- 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
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 313
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 313
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims abstract description 64
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 57
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 44
- 239000008199 coating composition Substances 0.000 claims description 29
- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- PJWWRFATQTVXHA-UHFFFAOYSA-N Cyclohexylaminopropanesulfonic acid Chemical compound OS(=O)(=O)CCCNC1CCCCC1 PJWWRFATQTVXHA-UHFFFAOYSA-N 0.000 claims description 26
- 238000009826 distribution Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000000565 sealant Substances 0.000 claims description 21
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- XNPKNHHFCKSMRV-UHFFFAOYSA-N 4-(cyclohexylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCNC1CCCCC1 XNPKNHHFCKSMRV-UHFFFAOYSA-N 0.000 claims description 12
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical class O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000005227 gel permeation chromatography Methods 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- MKWKNSIESPFAQN-UHFFFAOYSA-N N-cyclohexyl-2-aminoethanesulfonic acid Chemical compound OS(=O)(=O)CCNC1CCCCC1 MKWKNSIESPFAQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000013212 metal-organic material Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- -1 cycloaliphatic Chemical group 0.000 description 18
- 150000003254 radicals Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- SHAMRMCOVNDTCS-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC(O)C[N+](C)(C)C SHAMRMCOVNDTCS-UHFFFAOYSA-M 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
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 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
- 150000004985 diamines Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 150000003673 urethanes Chemical class 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
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-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
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-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
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- AGJCSCSSMFRMFQ-UHFFFAOYSA-N 1,4-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(C(C)(C)N=C=O)C=C1 AGJCSCSSMFRMFQ-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
- 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
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- HXYDAOXNYINGCS-UHFFFAOYSA-J 2-ethylhexanoate;tin(4+) Chemical compound [Sn+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O HXYDAOXNYINGCS-UHFFFAOYSA-J 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- ZDKYYMRLZONTFK-UHFFFAOYSA-N 3,4-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1CC2(CN=C=O)C(CN=C=O)CC1C2 ZDKYYMRLZONTFK-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
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-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 class CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-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
- BRKFTWHPLMMNHF-UHFFFAOYSA-N 5-amino-2-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C=C1S(O)(=O)=O BRKFTWHPLMMNHF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BHCFVCRRNLIOGM-UHFFFAOYSA-J C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] BHCFVCRRNLIOGM-UHFFFAOYSA-J 0.000 description 1
- UFGJHTCLALMYIL-UHFFFAOYSA-N CCCCP(CCCC)(CCCC)CCCC.F Chemical compound CCCCP(CCCC)(CCCC)CCCC.F UFGJHTCLALMYIL-UHFFFAOYSA-N 0.000 description 1
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- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical class O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
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- 239000006224 matting agent Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical class CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
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- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 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
- 238000010992 reflux Methods 0.000 description 1
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- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- HJBZFPLBRXFZNE-UHFFFAOYSA-M tetrabutylphosphanium fluoride hydrofluoride Chemical compound F.[F-].CCCC[P+](CCCC)(CCCC)CCCC HJBZFPLBRXFZNE-UHFFFAOYSA-M 0.000 description 1
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- 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 1
- XREKCAGAPAEVFE-UHFFFAOYSA-J tri(hexadecanoyloxy)stannyl hexadecanoate Chemical compound [Sn+4].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O XREKCAGAPAEVFE-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 235000005074 zinc chloride Nutrition 0.000 description 1
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- 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
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to modified polyisocyanates and to the use thereof, in particular as crosslinking components for water-soluble or water-dispersible coatings. The modified polyisocyanate comprises an iminooxadiazinedione structure and an isocyanurate structure, wherein the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure is not less than 1: 5; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate; the modified polyisocyanate is obtainable from a reaction comprising: a sulfamic acid, a polyisocyanate; a tertiary amine; and optionally a polyether alcohol containing ethylene oxide groups. The coatings comprising the modified polyisocyanates of the invention have good hand-stirring properties.
Description
Technical Field
The invention relates to modified polyisocyanates and to the use thereof, in particular as crosslinking components for water-soluble or water-dispersible coatings.
Background
In response to increasingly stringent environmental regulations in various countries, modified polyisocyanates which are water-dispersible have recently emerged as being of increasing importance in various fields of application. Water-dispersible modified polyisocyanates are frequently used as crosslinking components for aqueous two-component coatings or aqueous dispersion adhesives, sealants. Water-dispersible modified polyisocyanates are used to crosslink aqueous dispersions in textile finishing or formaldehyde-free textile printing inks and, in addition, as auxiliaries for the wet-strengthening treatment of paper (cf. for example EP-A0959087 and the documents cited therein).
At present, water-dispersible modified polyisocyanates can be broadly classified into two types: nonionic modification and ionic modification. Nonionic modified polyisocyanates, particularly polyether modified polyisocyanates, are widely used but still have many disadvantages. For example, due to the high viscosity to be overcome during dispersion, it is only possible to apply considerable shear forces (e.g. high speed stirring) to disperse them homogeneously in water. For another example, when the polyether-modified polyisocyanate is used as a crosslinking agent in an aqueous two-component coating, in order to achieve better dispersibility, a large amount of polyether is generally introduced, so that on one hand, the water resistance of a coating formed by the coating is permanently influenced, on the other hand, the concentration of isocyanate in the polyether-modified polyisocyanate is remarkably reduced, and the crosslinking density is reduced.
In order to overcome the above disadvantages, attempts have been made to use ionically modified polyisocyanates.
Water-dispersible carboxylic acid group-modified polyisocyanates are obtained, for example, using carboxylic acid group-modified polyisocyanates (EP-A0443138, EP-A0510438 and EP-A0548669). The carboxylic acid group-modified polyisocyanates can be dispersed in water by stirring without using high shear forces, but they have poor storage stability, especially after neutralization of the carboxylic acid groups. And, since the carboxylate group of the carboxylic acid group-modified polyisocyanate has a certain catalytic activity, the isocyanate group in the carboxylic acid group-modified polyisocyanate starts to polymerize at room temperature, for example, trimerization to polyisocyanurate to form an α -polyamide structure, thereby leading to gelation and poor storage stability of the carboxylic acid group-modified polyisocyanate.
And water-dispersible sulfonic acid group-modified polyisocyanates obtained by, for example, sulfonic acid group-modified polyisocyanates. CN101754990A discloses a method for modifying polyisocyanate by using 4-aminotoluene-2-sulfonic acid containing benzene ring, and the water dispersibility of the obtained sulfonic acid group modified polyisocyanate is better than that of carboxylic acid group modified polyisocyanate, but the existence of benzene ring reduces the yellowing resistance of the coating formed by the polyisocyanate. CN1190450C discloses the preparation of modified polyisocyanates using 3-cyclohexylaminopropane-1-sulfonic acid and 2- (cyclohexylamino) -ethanesulfonic acid as hydrophilic modification agents, tertiary amines as phase transfer catalysts and neutralizing agents. CN104448232 discloses the preparation of modified polyisocyanates using 4- (cyclohexylamino) -butanesulfonic acid as hydrophilic modifying agent and tertiary amines as phase transfer catalyst.
The sulfonic acid group-modified polyisocyanate can be dispersed in water without requiring a high shearing force, but in the actual operation process, the constructor still needs to dilute the sulfonic acid group-modified polyisocyanate to 70 to 80% with a solvent to reduce the viscosity thereof, mix it with other paint components, and apply manual stirring to disperse the mixture to obtain the paint. The addition of the solvent can obviously increase the VOC content of the coating and cause damage to the environment and human bodies.
Therefore, there is a need in the industry for a modified polyisocyanate that has good hand stirring and dispersibility without the need for solvent dilution.
Disclosure of Invention
The object of the present invention is to provide modified polyisocyanates and their use, in particular as crosslinking components for water-soluble or water-dispersible coatings.
The modified polyisocyanate according to the present invention comprises an iminooxadiazinedione structure and an isocyanurate structure in a weight ratio of not less than 1: 5; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate; the modified polyisocyanate is obtainable from a reaction comprising:
a. at least one sulfamic acid;
b. at least one polyisocyanate;
c. at least one tertiary amine; and
d. optionally a polyether alcohol containing ethylene oxide groups.
According to one aspect of the present invention, there is provided a process for the preparation of a modified polyisocyanate according to the present invention by reacting component a), component b) and optionally component d) in the presence of component c) to obtain said modified polyisocyanate.
According to a further aspect of the present invention, there is provided the use of the modified polyisocyanates provided according to the invention as starting components in the preparation of polyurethanes.
According to a further aspect of the present invention, there is provided the use of the modified polyisocyanates provided according to the invention as crosslinking components for water-soluble or water-dispersible coatings, adhesives or sealants.
According to a further aspect of the present invention, there is provided the use of the modified polyisocyanates provided according to the invention as starting components for preparing sealant-blocked polyisocyanates.
According to a further aspect of the present invention there is provided a coating, adhesive or sealant comprising a modified polyisocyanate provided according to the present invention.
According to yet another aspect of the present invention, there is provided a substrate coated with a coating, adhesive or sealant provided according to the present invention.
According to a further aspect of the present invention there is provided the use of a modified polyisocyanate as provided according to the present invention to improve the hand-rub properties of a coating, adhesive or sealant.
According to a further aspect of the present invention, there is provided the use of the modified polyisocyanates provided according to the invention as crosslinking components in water-soluble or water-dispersible aqueous two-component coating compositions.
According to yet another aspect of the present invention, there is provided an aqueous two-component coating composition comprising: at least one aqueous hydroxyl resin dispersion, at least one modified polyisocyanate provided according to the invention, optional auxiliaries and optional additives.
According to a further aspect of the present invention, there is provided a process for the preparation of an aqueous two-component coating composition comprising the steps of: the aqueous two-component coating compositions are obtained by mixing the aqueous hydroxyl resin dispersion, optional auxiliaries and optional additives in any desired manner to give a mixture, mixing the modified polyisocyanates provided according to the invention with the mixture and stirring by hand.
According to yet another aspect of the present invention, there is provided a product comprising a substrate and a coating layer formed by applying the aqueous two-component coating composition provided according to the present invention onto the substrate.
According to a further aspect of the present invention, there is provided a method of manufacturing a product by applying the aqueous two-component coating composition provided according to the present invention to a substrate, followed by curing and drying.
The modified polyisocyanate is water-soluble or water-dispersible, can be directly mixed with other coating components without being diluted by a solvent, can be uniformly dispersed in a resin system by simple manual stirring to obtain a coating, and the coating formed by the coating has good gloss and transparency.
The modified polyisocyanates do not require the addition of solvents for dispersion during the hybrid preparation of coatings, adhesives or sealants comprising the modified polyisocyanates of the invention, and therefore the coatings, adhesives or sealants prepared have a low VOC content.
Therefore, the invention actually provides the modified polyisocyanate with good manual stirring performance and good dispersibility, and the coating formed by the modified polyisocyanate and the coating containing the modified polyisocyanate have high gloss and good transparency.
Detailed Description
The present invention provides a modified polyisocyanate comprising an iminooxadiazinedione structure and an isocyanurate structure in a weight ratio of not less than 1: 5; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate; the modified polyisocyanate is obtainable from a reaction comprising:
a. at least one sulfamic acid;
b. at least one polyisocyanate;
c. at least one tertiary amine; and
d. optionally a polyether alcohol containing ethylene oxide groups. The invention also provides a method for preparing the modified polyisocyanate, application of the modified polyisocyanate in preparing polyurethane or preparing sealant blocked polyisocyanate, application in preparing water-soluble or water-dispersible coating, adhesive or sealant and application in improving the hand stirring property of the coating, the adhesive or the sealant, the coating, the adhesive or the sealant containing the modified polyisocyanate, in particular application of the modified polyisocyanate in wood coating, a preparation method of an aqueous two-component coating composition, a product obtained by coating the coating on a substrate and a method for manufacturing the product.
The number average molecular weight of the modified polyisocyanates according to the invention is determined by gel permeation chromatography and DIN 55672-1: 2016-03, and is obtained by taking polystyrene as a standard substance and taking tetrahydrofuran as an eluent for testing.
Sulfonate according to the invention means SO having a molecular weight of 80g/mol3 2-。
The viscosity of the modified polyisocyanates according to the invention is in accordance with DIN EN ISO 3219: 1994-10 at 23 deg.C for 10s-1Is measured at a shear rate of (2).
The term "polyurethane" as used herein refers to polyurethaneurea and/or polyurethane polyurea and/or polythiourethane.
The term "molecular weight distribution" as used herein refers to the ratio of the weight average molecular weight to the number average molecular weight of the modified polyisocyanate.
Modified polyisocyanates
The modified polyisocyanates of the invention may also be referred to as mixtures of modified polyisocyanates.
The modified polyisocyanate is water dispersible or water soluble.
The molecular weight distribution of the modified polyisocyanate is preferably 1.2 to 2.0.
The iminooxadiazinedione structure of the modified polyisocyanates corresponds to formula II:
wherein R is4，R5And R6Independently of one another, identical or different, they may be radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanates, radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanates, radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanates and radicals which are obtained by reaction with sulfamic acid, radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanates and radicals which are obtained by reaction with sulfamic acid.
The isocyanurate structure of the modified polyisocyanate is according to formula III:
wherein R is7，R8And R9Independently of one another, identical or different, are either radicals which are obtained by removing an isocyanate group from an aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanate, radicals which are obtained by removing an isocyanate group from an aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanate, radicals which are obtained by removing an isocyanate group from an aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanate and radicals which are obtained by reacting sulfamic acidThe radicals obtained here may also be radicals obtained by reaction of radicals obtained by removal of one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanates with sulfamic acid.
Wherein R is4、R5、R6、R7、R8And R9May be each independently, the same or different.
The weight ratio of iminooxadiazinedione structures to isocyanurate structures of the modified polyisocyanates is preferably from 1: 5 to 1: 1, most preferably from 1: 5 to 1: 2.
The number average molecular weight of the modified polyisocyanate is preferably 700g/mol to 1500g/mol, more preferably 750g/mol to 1200g/mol, still more preferably 750g/mol to 1000g/mol, and most preferably 750g/mol to 900 g/mol. Number average molecular weight according to gel permeation chromatography and DIN 55672-1: 2016-03, and is obtained by taking polystyrene as a standard substance and taking tetrahydrofuran as an eluent for testing.
The weight average molecular weight of the modified polyisocyanate is determined by gel permeation chromatography and DIN 55672-1: 2016-03, and is obtained by taking polystyrene as a standard substance and taking tetrahydrofuran as an eluent for testing.
The total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is preferably 4.1 to 20% by weight, more preferably 4.1 to 16% by weight, most preferably 4.1 to 11% by weight, relative to the total weight of the modified polyisocyanate.
The molecular weight distribution of the modified polyisocyanate is preferably 1.3 to 1.7, most preferably 1.3 to 1.6.
The sum of the weights of the iminooxadiazinedione structures and isocyanurate structures of the modified polyisocyanates is preferably not less than 5% by weight, relative to the total weight of the modified polyisocyanates.
The amount of sulfonate groups of the modified polyisocyanate is preferably 0.1 to 7.0 wt.%, most preferably 0.9 to 1.5 wt.%, relative to the total weight of the modified polyisocyanate.
The viscosity of the modified polyisocyanate is preferably greater than 2250mpa.s and not more than 30000mpa.s, most preferably 2300mPa.s-15000mPa.s, viscosity according to DIN EN ISO 3219: 1994-10 at 23 deg.C for 10s-1And viscosity is measured in the case that the modified polyisocyanate does not contain a solvent.
The isocyanate group content of the modified polyisocyanate is preferably 7% by weight to 23% by weight, further preferably 19% by weight to 22% by weight, most preferably 19.5% by weight to 22% by weight, relative to the total weight of the modified polyisocyanate.
The color of the modified polyisocyanate is preferably from 16 to 31.
Component a) sulfamic acid
The sulfamic acid of component a) is preferably according to formula I:
wherein the content of the first and second substances,
R1and R2Each independently is hydrogen, a substituted or unsubstituted and/or heteroatom-containing aliphatic group having 1 to 18 carbon atoms, a substituted or unsubstituted and/or heteroatom-containing cycloaliphatic group having 3 to 18 carbon atoms, a substituted or unsubstituted and/or heteroatom-containing aromatic group having 1 to 18 carbon atoms; r1And R2Reacting to form an alicyclic group having 3 to 8 carbon atoms or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom; r3Is a linear or branched aliphatic group having 2 to 8 carbon atoms.
The R is1And R2The reaction forms an alicyclic group having 3 to 8 carbon atoms or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom, which is preferably further substituted.
The R is3Preferably a linear or branched aliphatic group having 2 to 4 carbon atoms, further preferably a linear or branched aliphatic group having 2 to 3 carbon atoms, most preferably a linear or branched aliphatic group having 3 carbon atoms.
The sulfamic acid may be one or any mixture of several sulfamic acids according to formula I.
The sulfamic acid is preferably one or more of the following: 3-cyclohexylaminopropane-1-sulfonic acid, 4-cyclohexylamino-1-butanesulfonic acid and 2-cyclohexylaminoethane-1-sulfonic acid, further preferably one or more of the following: 3-cyclohexylaminopropane-1-sulfonic acid and 4-cyclohexylamino-1-butanesulfonic acid, with 3-cyclohexylaminopropane-1-sulfonic acid being most preferred.
The amount of sulfamic acid is preferably from 0.28 to 22 wt. -%, further preferably from 1.5 to 3.5 wt. -%, yet preferably from 2 to 3 wt. -%, most preferably from 2.2 to 2.9 wt. -%, relative to the total weight of the components a) and b).
The amount of sulfonate groups of the sulfamic acid is preferably from 0.1% by weight to 7% by weight, relative to the total weight of the modified isocyanate.
Component b) polyisocyanates
The polyisocyanate in the present invention means a raw material component for preparing the modified polyisocyanate.
The polyisocyanate preferably comprises at least one iminooxadiazinedione structure and at least one isocyanurate structure.
The iminooxadiazinedione structure preferably corresponds to formula IV:
wherein R is10，R11And R12Independently of one another, identical or different, are both radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanates and also radicals which are obtained by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanates.
The isocyanurate structure is according to formula V:
wherein R is13，R14And R15Independently of one another, identical or different, are radicals which are obtainable by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic diisocyanates and also radicals which are obtainable by removing one isocyanate group from aliphatic, cycloaliphatic, aromatic and/or araliphatic oligomeric polyisocyanates.
Wherein R is10、R11、R12、R13、R14And R15May be the same or different from each other independently.
The weight ratio of iminooxadiazinedione structures to isocyanurate structures of the polyisocyanates is preferably greater than 1: 5, more preferably greater than 1: 5 and not greater than 1: 1, still more preferably from 1: 4 to 1: 1, most preferably from 1: 4 to 1: 2.
The number average molecular weight of the polyisocyanate is preferably 600g/mol to 1400g/mol, more preferably 700g/mol to 1200g/mol, still more preferably 750g/mol to 1200g/mol, and most preferably 950g/mol to 1200 g/mol. Number average molecular weight according to gel permeation chromatography and DIN 55672-1: 2016-03, and is obtained by taking polystyrene as a standard substance and taking tetrahydrofuran as an eluent for testing.
The total amount of molecules having a number average molecular weight of more than 2700g/mol in the polyisocyanate is 2.5 to 17 wt. -%, further preferably 4.1 to 15 wt. -%, yet preferably 4.1 to 12 wt. -%, most preferably 5 to 10 wt. -%, relative to the total weight of the polyisocyanate.
The sum of the weights of the iminooxadiazinedione and isocyanurate structures of the polyisocyanates is preferably not less than 5% by weight, relative to the total weight of the polyisocyanate.
The monomeric diisocyanate content of the polyisocyanate is preferably less than 1% by weight, most preferably less than 0.5% by weight, relative to the total weight of the polyisocyanate.
The viscosity of the polyisocyanate is preferably 500mPa.s-15000mpa.s, further preferably 700mpa.s to 10000mpa.s, most preferably 700mpa.s to 6000mpa.s, viscosity according to DIN EN ISO 3219: 1994-10 at 23 deg.C for 10s-1Is measured at a shear rate of (2).
The amount of the polyisocyanate is preferably not less than 5% by weight, relative to the total weight of the components of the reaction for preparing the modified polyisocyanate.
The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates and aromatic polyisocyanates.
The polyisocyanate may further comprise one or more of the following in addition to the isocyanurate structure and iminooxadiazinedione structure: biurets, uretdiones, and allophanates.
The polyisocyanates are preferably composed of at least two diisocyanates and are prepared by modification of simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates, as described, for example, in the following documents: J.Prakt.chem.336(1994)185-200, DE-A1670666, DE-A1954093, DE-A2414413, DE-A242532, DE-A2641380, DE-A3700209, DE-A3900053 and DE-A3928503 or EP-A0336205, EP-A0339396 and EP-A0798299. Any of the diisocyanates that can be prepared by phosgenation or by phosgene-free processes, such as the thermal cracking of urethanes.
The weight average molecular weight of the diisocyanate is preferably 140-400.
The diisocyanate is preferably one or more of the following: 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane (HDI), 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethylpentane, 2, 4-trimethyl-1, 6-diisocyanatohexane, 2, 4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 1, 3-bis (isocyanatomethyl) -cyclohexane, 1, 4-bis (isocyanatomethyl) -cyclohexane, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4 ' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4 (3) isocyanato-methylcyclohexane, bis (isocyanatomethyl) -norbornane, 1, 3-and 1, 4-bis (2-isocyanato-prop-2-yl) -benzene (TMXDI), 2, 4-diisocyanatotoluene, 2, 6-diisocyanatotoluene, 2, 4 ' -diisocyanatodiphenylmethane, 4 ' -diisocyanatodiphenylmethane and 1, 5-diisocyanatonaphthalene.
The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates and alicyclic polyisocyanates, with aliphatic polyisocyanates being more preferred, and one or more of the following being even more preferred: derivatives of hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate and 4, 4' -diisocyanatodicyclohexylmethane having an isocyanurate structure and an iminooxadiazinedione structure, and also preferably one or more of the following: derivatives of hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, and 4, 4' -diisocyanatodicyclohexylmethane having an isocyanurate structure and an iminooxadiazinedione structure, most preferably one or more of the following: a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure.
The polyisocyanate is preferably hydrophobic.
When the system comprises two or more polyisocyanates, the number average molecular weight of the polyisocyanate, the total amount of molecules having a number average molecular weight of more than 2700g/mol, the weight ratio of the iminooxadiazinedione structure and the isocyanurate structure of the polyisocyanate, and the viscosity all refer to average values.
When the system comprises two or more polyisocyanates, it is most preferred that the weight ratio of iminooxadiazinedione structures to isocyanurate structures of each polyisocyanate corresponds to greater than 1: 5, preferably greater than 1: 5 and not greater than 1: 1, further preferably from 1: 4 to 1: 1, most preferably from 1: 4 to 1: 2.
Component c) tertiary amines
The tertiary amines of the present invention are useful for neutralizing the sulfonic acid groups of sulfamic acid.
The tertiary amine is preferably one or more of the following: tertiary monoamines, tertiary diamines and other tertiary amines containing groups reactive toward isocyanates.
The tertiary monoamine is preferably one or more of the following: trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N-methylpiperidine and N, N-dimethylcyclohexylamine.
The tertiary diamine is preferably one or more of the following: 1, 3-bis- (dimethylamino) -propane, 1, 4-bis- (dimethylamino) -butane and N, N' -dimethylpiperazine.
The tertiary amine is most preferably N, N-dimethylcyclohexylamine.
The further tertiary amines comprising groups reactive toward isocyanates are preferably neutralizing amines, preferably alkanolamines, such as dimethylethanolamine, methyldiethanolamine and/or triethanolamine.
The molar equivalent ratio of the tertiary amine to the sulfonate group of the sulfamic acid is preferably 0.3 to 1.9, most preferably 0.6 to 1.4.
The amount of tertiary amine is sufficient to catalyze the reaction of components a, b and optionally component d, but other conventional catalysts known in polyurethane chemistry are optionally used to accelerate the reaction in the process of the invention. The conventional catalyst is preferably one or more of the following: other tertiary amines and metal salts.
The other tertiary amines are preferably one or more of the following: triethylamine, pyridine, picoline, benzyldimethylamine, N-endo-ethylene piperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N-dimethyl-aminocyclohexane and N, N' -dimethylpiperazine.
The metal salt is preferably one or more of the following: iron chloride, aluminum tris (ethyl-acetoacetate), zinc chloride, zinc n-octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylhexanoate, zinc stearate, zinc naphthenate, zinc acetylacetonate, tin n-octanoate, tin 2-ethyl-1-hexanoate, tin ethylhexanoate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin dilaurate, dioctyltin diacetate, and molybdenum glycolate.
The amount of the conventional catalyst is preferably from 0.001 wt% to 2 wt%, most preferably from 0.005 wt% to 0.5 wt%, relative to the total weight of the components of the reaction.
Component d) polyether alcohols containing ethylene oxide groups
The ethylene oxide group content of the polyether alcohol comprising an ethylene oxide group is preferably from 0 to 17% by weight, further preferably from 0 to 13% by weight, most preferably from 0 to 5% by weight, relative to the total weight of the components of the reaction.
The polyether alcohols containing ethylene oxide groups preferably contain a statistical average of from 5 to 30, most preferably from 7 to 25, ethylene oxide groups per molecule.
The polyether alcohols containing oxirane groups can be obtained in a known manner by alkoxylation of suitable starter molecules, for example Ullmanns encyclop. diederert technischen Chemie, 4 th edition, volume 19, VerlagChemie Weinheim, pages 31 to 38.
The suitable starter molecules are preferably one or more of the following: saturated monoalcohols, unsaturated alcohols, aromatic alcohols, araliphatic alcohols, secondary monoamines and heterocyclic secondary amines.
The saturated monoalcohol is preferably one or more of the following: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols, nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols, hydroxymethylcyclohexane, 3-ethyl-3-oxetanemethanol and tetrahydrofurfuryl alcohol.
The unsaturated alcohol is preferably one or more of the following: allyl alcohol, 1-dimethyl-allyl alcohol and oleyl alcohol.
The aromatic alcohol is preferably one or more of the following: phenol, the isomeric cresols and methoxyphenols.
The araliphatic alcohol is preferably one or more of the following: benzyl alcohol, anisol and cinnamyl alcohol.
The secondary monoamine is preferably one or more of the following: dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-N-butylamine, diisobutylamine, bis (2-ethylhexyl) -amine, N-methylcyclohexylamine, N-ethylcyclohexylamine, and dicyclohexylamine.
The heterocyclic secondary amine is preferably one or more of the following: morpholine, pyrrolidine, piperidine and 1H-pyrazole.
The suitable starter molecules are further preferably saturated monoalcohols having from 1 to 4 carbon atoms, most preferably methanol.
Alkylene oxides suitable for the alkoxylation reaction, in particular ethylene oxide and/or propylene oxide, can be used in the alkoxylation reaction in any order or as a mixture.
The polyether alcohol containing an ethylene oxide group can be any mixture of one or several polyether alcohols containing an ethylene oxide group.
The alkylene oxide units in the polyether alcohol comprising ethylene oxide groups preferably comprise not less than 30 mol%, most preferably not less than 40 mol% of ethylene oxide groups.
The polyether alcohol containing ethylene oxide groups is most preferably a polyethylene glycol-methyl ether alcohol containing a statistical average of 7 to 30, most preferably 7 to 25 ethylene oxide groups per molecule.
The polyether alcohols comprising ethylene oxide groups according to the invention may be additionally added or the polyisocyanates may already comprise ethylene oxide polyether units. When the polyisocyanate already contains ethylene oxide polyether units, said polyisocyanate is a polyisocyanate which is hydrophilically modified with an ethylene oxide polyether alcohol, prepared for example by the process described in EP-A0959087, page 2, lines 25-46.
Solvent(s)
The reaction components for preparing the modified polyisocyanate may further comprise a solvent.
The solvents are conventional solvents known to be useful in the preparation of modified polyisocyanates, preferably one or more of the following: ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, 3-methoxy N-butyl ethyl ester, 1-methoxyprop-2-yl acetate, 3-methoxy-N-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white spirit, more highly substituted aromatic compounds, carbonates, lactones, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl ether ethyl ester, diethylene glycol butyl ether ethyl ester, N-methylpyrrolidone, and N-methylcaprolactam.
The more highly substituted aromatic compounds are preferably solvent naphthas under the trade name Solvesso, Isopar, Nappar and Shellsol.
The carbonate is preferably one or more of the following: dimethyl carbonate, diethyl carbonate, 1, 2-ethylene carbonate and 1, 2-propylene carbonate.
The lactone is preferably one or more of beta-propiolactone, gamma-butyrolactone, epsilon-caprolactone and epsilon-methyl caprolactone.
The modified polyisocyanate is preferably obtained by a reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and
c. a tertiary amine;
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 1, the number average molecular weight of the modified polyisocyanate is 700g/mol-1500g/mol, and the molecular weight distribution is 1.2-2.0; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate.
The modified polyisocyanates are further preferably obtained by reaction of a mixture comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and
c. a tertiary amine;
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 1, the number average molecular weight of the modified polyisocyanate is 700g/mol-1200g/mol, and the molecular weight distribution is 1.2-2.0; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1% to 16% by weight, relative to the total weight of the modified polyisocyanate.
The modified polyisocyanates are also preferably obtained by reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and
c. a tertiary amine;
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 1, the number average molecular weight of the modified polyisocyanate is 700g/mol-1200g/mol, and the molecular weight distribution is 1.2-2.0; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1% to 15% by weight relative to the total weight of the modified polyisocyanate; the modified polyisocyanate has a sulfonate group in an amount of 0.9 to 1.5% by weight and an isocyanate group in an amount of 19 to 22% by weight, relative to the total weight of the modified polyisocyanate; the viscosity of the modified polyisocyanate is 2300 to 15000 mPa.s.
The modified polyisocyanate is most preferably obtained by a reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid in an amount of from 0.28% to 22% by weight, relative to the total weight of said component a and component b;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure, the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of component b) being from 1: 5 to 1: 1, most preferably from 1: 4 to 1: 2; and
c. n, N-dimethylcyclohexylamine in a molar equivalent ratio of from 0.3 to 1.9, based on the sulfonate groups of component a);
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 2, the number average molecular weight of the modified polyisocyanate is 750g/mol-900g/mol, and the molecular weight distribution is 1.3-1.6; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1% to 15% by weight, relative to the total weight of the modified polyisocyanate.
The modified polyisocyanate is most preferably obtained by a reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid in an amount of from 0.28% to 22% by weight, relative to the total weight of said component a and component b;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure, the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of component b) being from 1: 5 to 1: 1, most preferably from 1: 4 to 1: 2; and
c. n, N-dimethylcyclohexylamine in a molar equivalent ratio of from 0.3 to 1.9, based on the sulfonate groups of component a);
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 2, the number average molecular weight of the modified polyisocyanate is 750g/mol-900g/mol, and the molecular weight distribution is 1.3-1.6; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1% to 15% by weight relative to the total weight of the modified polyisocyanate; the modified polyisocyanate has a sulfonate group in an amount of 0.9 to 1.5% by weight and an isocyanate group in an amount of 19.5 to 22% by weight, relative to the total weight of the modified polyisocyanate; the viscosity of the modified polyisocyanate is 2300 to 15000 mPa.s.
Process for preparing modified polyisocyanates
The preparation method of the modified polyisocyanate comprises the following steps: in the presence of component a), component b), component c) and optionally component d) at a temperature of from 40 ℃ to 150 ℃ in such a way that the molar equivalent ratio of NCO groups to groups reactive toward NCO groups is maintained in the range from 2: 1 to 400: 1.
The reaction temperature is preferably 50 ℃ to 130 ℃.
The molar equivalent ratio of NCO groups to NCO-reactive groups is preferably from 4: 1 to 250: 1, most preferably until the reaction has reached the theoretical calculated NCO content.
The modified polyisocyanate is clear, colorless or nearly colorless.
Applications of
The modified polyisocyanates are preferably used in the form of aqueous emulsions.
The polyisocyanates according to the invention are preferably used as crosslinking components for water-soluble or water-dispersible coating, adhesive or sealant components which have groups reactive toward isocyanate groups, in particular alcoholic hydroxyl groups, in the production of coatings based on such aqueous coating, adhesive or sealant compositions.
When the modified polyisocyanates of the invention are used as crosslinking components, for components of water-soluble or water-dispersible coatings, the molar ratio of NCO groups of the modified polyisocyanates to NCO-reactive groups, in particular alcoholic hydroxyl groups, is preferably from 0.5: 1 to 2: 1.
When the modified polyisocyanates of the invention are used as crosslinking components in water-soluble or water-dispersible adhesives or sealants, they can optionally be incorporated in small amounts into nonfunctional water-soluble or water-dispersible adhesives or sealants in order to achieve very specific properties, for example as additives for improving tack. For example as papermaking aids or additives free of absorbable halides, for use in inorganic building materials such as concrete or mortar.
The coating, adhesive or sealant comprising the modified polyisocyanate may further comprise a polyisocyanate different from the modified polyisocyanate. The polyisocyanate other than the modified polyisocyanate is preferably added to the modified polyisocyanate before the modified polyisocyanate is mixed with the resin component.
The amount of the polyisocyanate different from the modified polyisocyanate is preferably such that the properties of the coating, adhesive or sealant comprising the aqueous hydroxyl resin dispersion and the modified polyisocyanate are not affected. For this combination, the modified polyisocyanate of the present invention acts as an emulsifier for polyisocyanates other than the modified polyisocyanate.
Use in the preparation of polyurethanes
The modified polyisocyanates can also be used in the form of a sealer block in aqueous one-component polyurethane systems. Suitable blocking agents are, for example, diethyl malonate, ethyl acetoacetate, acetoxime, butanone oxime, epsilon-caprolactam, 3, 5-dimethylpyrazole, 1, 2, 4-triazole, dimethyl-1, 2, 4-triazole, imidazole or any mixtures of these blocking agents.
The modified polyisocyanate has excellent emulsibility in water, can be uniformly distributed, and a coating formed by polyurethane containing the modified polyisocyanate has excellent optical properties, especially high surface gloss and high transparency.
Method of manufacturing a product
The coating may be by mechanical means known to those skilled in the art or by use of a two-component spray gun.
The substrate may be any substrate, preferably metal, wood, alloy, inorganic material, glass, stone, ceramic raw material, concrete, rigid synthetic material, flexible synthetic material, textile, leather or paper, most preferably wood, metal, alloy or inorganic material.
The substrate may optionally have a conventional primer before being coated.
Aqueous two-component coating composition
The aqueous hydroxyl resin dispersion is preferably a hydroxyl group-containing polyacrylate dispersion, and most preferably a hydroxyl group-containing polyacrylate dispersion having a weight average molecular weight of 1000-10000.
In principle, all compounds which are dissolved or dispersed in water and contain groups reactive toward isocyanates are suitable as reaction partners for the aqueous two-component coating compositions according to the invention, for example polyurethanes or polyureas, which are dispersed in water, the presence of active hydrogen atoms in the urethane or urea groups, which polyurethanes or polyureas can be crosslinked with modified polyisocyanates, are suitable as reaction partners.
The aqueous two-component coating compositions may optionally comprise auxiliaries and additives customary in the coating art, for example one or more of flow auxiliaries, color pigments, fillers, defoamers, cosolvents, matting agents and emulsifiers.
The aqueous two-component coating composition dries at room temperature to form a coating with good properties.
The aqueous two-component coating composition can also be dried at elevated temperature or dried at a temperature of up to 260 ℃.
The aqueous two-component coating composition may be a wood coating, a textile coating, a plastic coating, an architectural coating, or a metal coating, most preferably a wood coating.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
As used in this specification, the terms "a", "an" and "the" are intended to include "at least one" or "one or more" unless otherwise indicated. For example, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments.
As used herein, "and/or" means one or all of the referenced elements.
As used herein, "comprising" and "comprises" encompass the presence of only the recited elements as well as the presence of other, non-recited elements in addition to the recited elements.
All percentages in the present invention are by weight unless otherwise indicated.
The analytical measurements according to the invention were carried out at 23 ℃ unless otherwise stated.
The weight ratio of iminooxadiazinedione structures to isocyanurate structures in the polyisocyanate was determined by 13C NMR. The test instrument was Bruker DPX-400. Iminooxadiazinedione structure: the weight ratio of isocyanurate structures is 1: (integrated area @148.4 ppm)/(integrated area @147.9ppm + integrated area @144.5ppm + integrated area @135.3 ppm). The iminooxadiazinedione structure has the same molecular weight as the isocyanurate structure.
Viscosity according to DIN EN ISO 3219: 1994-10 at 23 deg.C for 10s-1The MV-DIN rotor was selected, determined at a shear rate of (1).
Isocyanate group (NCO) content according to DIN-EN ISO 11909: 2007-05 assay.
Color value test standard: DIN-EN 1557: 1997-03.
Gloss test standard: GB/T9754-2007.
Haze test standard: ASTM E430-11.
Raw materials and reagents
Polyisocyanate P1: 850g of Hexamethylene Diisocyanate (HDI) was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas blowing tube and a dropping funnel under a nitrogen atmosphere, the flask was heated to 65 ℃ with stirring, and 5.5g of trimethyl-2-methyl-2-hydroxyethylammonium hydroxide (a solution diluted to 5% by weight with isobutanol) as a catalyst was added thereto, and when the NCO content of the reaction mixture was 38% by weight, 1.1g of di-n-butyl phosphate was added to stop the reaction. The unreacted monomers were removed by means of a thin film evaporator to obtain a polyisocyanate P1 having a nonvolatile content of 100% by weight, a viscosity of 3000 mPas (23.5 ℃ C.), an NCO content of 21.7% by weight, a HDI monomer concentration of 0.25% by weight, and a weight ratio of iminooxadiazinedione structures to isocyanurate structures of 1: 20.28.
Polyisocyanate P2: the reaction was terminated at 32% NCO in the reaction mixture by the method of P1 preparation. The unreacted monomers were removed by means of a thin film evaporator to give a polyisocyanate P2 having a nonvolatile content of 100% by weight, a viscosity of 16000 mPas (23.5 ℃ C.), an NCO content of 20% by weight, a HDI monomer concentration of 0.25% by weight, and a weight ratio of iminooxadiazinedione structures to isocyanurate structures of 1: 27.57.
Polyisocyanate P3: using the procedure for the preparation of P1, dibutyl phosphate was added to terminate the reaction at 43% NCO in tetrabutyl phosphonium fluoride solution (diluted to 50% with a 2: 1 isopropanol/methanol weight ratio solvent). The unreacted monomers were removed by means of a thin film evaporator to obtain a polyisocyanate P3 having a nonvolatile content of 100% by weight, a viscosity of 700 mPas (23.5 ℃ C.), an NCO content of 23.4% by weight, a HDI monomer concentration of 0.25% by weight, and a weight ratio of iminooxadiazinedione structures to isocyanurate structures of 1: 1.28.
Tetrabutyl phosphine fluoride solution: purchased from golden chemicals.
Isopropyl alcohol from Sigma-Aldrich.
Methanol from Sigma-Aldrich.
3-Cyclohexylaminopropane-1-sulfonic acid, purchased from Sigma-Aldrich.
N, N-dimethylcyclohexylamine: purchased from Sigma-Aldrich.
Trimethyl-2-methyl-2-hydroxyethyl ammonium hydroxide: Sigma-Aldrich.
Bayhydrol a 2470: aqueous hydroxyacrylate dispersions, available from scientific, germany.
BYK 028: silicone antifoam (a mixture of a defoaming polysiloxane and hydrophobic particles in polyethylene glycol) was purchased from BYK, germany.
BYK 346: wetting and leveling agents (polyether modified siloxane solutions) were purchased from BYK, germany.
BUTYL CELLOSOLVE: cosolvent, butyl cellosolve, available from dow chemical usa.
RHEOVIS PU 1291: hydrophobically modified ethoxylated urethane, rheology aid, associative thickener, available from basf, germany.
Modified polyisocyanate 1
60.35g (0.287eq) of polyisocyanate P2, 342g (1.9eq) of polyisocyanate P3, 11.30g (0.051eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 6.680g (0.053mol) of dimethylcyclohexylamine were stirred under dry nitrogen at 80 ℃ for 4 hours to give, after cooling to room temperature, a modified polyisocyanate 1 according to the invention having the following characteristic data, the modified polyisocyanate 1 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 21.46% by weight
Viscosity (23 ℃): 2300mPa · s
Color number (Hazen): 31
Sulfonate content: 0.98% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 2.12
Number average molecular weight (Mn): 773g/mol
Molecular weight distribution: 1.31
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 4.15% by weight
Content of ethylene oxide group: 0.0% by weight.
Modified polyisocyanates 2
225g (1.154eq) of polyisocyanate P1, 150g (0.833eq) of polyisocyanate P3, 14.80g (0.067eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 8.60g (0.068mol) of dimethylcyclohexylamine were stirred under dry nitrogen at 80 ℃ for 4 hours to give, after cooling to room temperature, a modified polyisocyanate 2 according to the invention having the following characteristic data, the modified polyisocyanate 2 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 19.94% by weight
Viscosity (23 ℃): 7209 mPas
Color number (Hazen): 16
Sulfonate content: 1.34% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 4.15
Number average molecular weight (Mn): 835g/mol
Molecular weight distribution: 1.32
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 5.51% by weight
Content of ethylene oxide group: 0.0% by weight.
Modified polyisocyanate 3
After stirring 133g (0.633eq) of polyisocyanate P2, 247g (1.372eq) of polyisocyanate P3, 10.76g (0.049eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 6.3g (0.050mol) of dimethylcyclohexylamine under dry nitrogen at 80 ℃ for 4 hours, a modified polyisocyanate 3 according to the invention having the following characteristic data is obtained after cooling to room temperature, the modified polyisocyanate 3 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 20.14% by weight
Viscosity (23 ℃): 5857 mPas
Color number (Hazen): 25
Sulfonate content: 0.98% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 2.3
Number average molecular weight (Mn): 870g/mol
Molecular weight distribution: 1.50
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 9.95% by weight
Content of ethylene oxide group: 0.0% by weight.
Modified polyisocyanate 4
200g (1.026eq) of polyisocyanate P2, 200g (1.111eq) of polyisocyanate P3, 11.3g (0.051eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 6.55g (0.052mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a modified polyisocyanate 4 according to the invention having the following characteristic data, the modified polyisocyanate 4 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 20.42% by weight
Viscosity (23 ℃): 7525 mPa.s
Color number (Hazen): 27
Sulfonate content: 0.98% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 3.23
Number average molecular weight (Mn): 887g/mol
Molecular weight distribution: 1.51
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 10.14% by weight
Content of ethylene oxide group: 0.0% by weight.
Modified polyisocyanate 5
228g (1.086eq) of polyisocyanate P2, 152g (0.8444eq) of polyisocyanate P3, 10.76g (0.09eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 6.3g (0.050mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a modified polyisocyanate 5 according to the invention having the following characteristic data, the modified polyisocyanate 5 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 19.18% by weight
Viscosity (23 ℃): 11340 mPas
Color number (Hazen): 22
Sulfonate content: 0.98% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 4.1
Number average molecular weight (Mn): 939g/mol
Molecular weight distribution: 1.64
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 15.94% by weight
Content of ethylene oxide group: 0.0% by weight.
Comparative modified polyisocyanate 1
400g (2.222eq) of polyisocyanate P3, 14.8g (0.067eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 8.70g (0.068mol) of dimethylcyclohexylamine were stirred under dry nitrogen at 80 ℃ for 4 hours and, after cooling to room temperature, gave a comparative modified polyisocyanate 1 which had the following characteristic data, the comparative modified polyisocyanate 1 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 21.46% by weight
Viscosity (23 ℃): 1905 mPas
Color number (Hazen): 42
Sulfonate content: 1.26% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 1.28
Number average molecular weight (Mn): 718g/mol
Molecular weight distribution: 1.13
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 0% by weight
Content of ethylene oxide group: 0.0% by weight.
Comparative modified polyisocyanate 2
428.7g (2.198eq) of polyisocyanate P1, 285.12g (1.584eq) of polyisocyanate P3, 20.32g (0.092eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 11.7g (0.090mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a comparative modified polyisocyanate 2 having the following characteristic data, the comparative modified polyisocyanate 2 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 20.9% by weight
Viscosity (23 ℃): 3501mPa · s
Color number (Hazen): 16
Sulfonate content: 0.98% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 4.15
Number average molecular weight (Mn): 787g/mol
Molecular weight distribution: 1.22
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 2.61% by weight
Content of ethylene oxide group: 0.0% by weight.
Comparative modified polyisocyanate 3
225g (1.154eq) of polyisocyanate P1, 150g (0.833eq) of polyisocyanate P3, 13.50g (0.061eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 8.0g (0.063mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a comparative modified polyisocyanate 3 having the following characteristic data, the comparative modified polyisocyanate 3 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 20.3% by weight
Viscosity (23 ℃): 5945 mPa.s
Color number (Hazen): 22
Sulfonate content: 1.23% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 4.15
Number average molecular weight (Mn): 804g/mol
Molecular weight distribution: 1.28
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 3.97% by weight
Content of ethylene oxide group: 0.0% by weight.
Comparative modified polyisocyanate 4
38g (0.181eq) of polyisocyanate P2, 342g (1.922eq) of polyisocyanate P3, 12.0g (0.054eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 7.0g (0.055mol) of dimethylcyclohexylamine were stirred under dry nitrogen at 80 ℃ for 4 hours to give, after cooling to room temperature, a comparative modified polyisocyanate 4 having the following characteristic data, the comparative modified polyisocyanate 4 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 21.43% by weight
Viscosity (23 ℃): 2137 mPas
Color number (Hazen): 16
Sulfonate content: 1.08% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 1.51
Number average molecular weight (Mn): 738g/mol
Molecular weight distribution: 1.19
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 1.94% by weight
Content of ethylene oxide group: 0.0% by weight.
Comparative modified polyisocyanate 5
718g (3.682eq) of polyisocyanate P1, 24.0g (0.108eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 14.0g (0.110mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a comparative modified polyisocyanate 5 which had the following characteristic data, the comparative modified polyisocyanate 5 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 19.76% by weight
Viscosity (23 ℃): 9361 mPas
Color number (Hazen): 18
Sulfonate content: 1.15% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 20.27
Number average molecular weight (Mn): 866g/mol
Molecular weight distribution: 1.33
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 6.06% by weight
Ethylene oxide content: 0.0% by weight.
Comparative modified polyisocyanate 6
718g (3.682eq) of polyisocyanate P1, 12.6g (0.057eq) of 3-cyclohexylaminopropane-1-sulfonic acid and 7.6g (0.060mol) of dimethylcyclohexylamine were stirred at 80 ℃ for 4 hours under dry nitrogen and, after cooling to room temperature, gave a comparative modified polyisocyanate 6 which had the following characteristic data, the comparative modified polyisocyanate 6 being a colorless, transparent solution and corresponding to the following characteristics:
solid content: 100% by weight
NCO content: 20.85% by weight
Viscosity (23 ℃): 5296 mPas
Color number (Hazen): 14
Sulfonate content: 0.61% by weight
Iminooxadiazinedione structure/isocyanurate structure: 1: 20.27
Number average molecular weight (Mn): 855g/mol
Molecular weight distribution: 1.31
Total amount of molecules having a number average molecular weight Mn of more than 2700 g/mol: 5.49% by weight
Ethylene oxide content: 0.0% by weight.
Method for preparing aqueous two-component coating compositions of examples and comparative examples
Preparing a component A: according to the formula listed in Table 1, a defoaming agent, a leveling agent, a cosolvent, a rheological aid and water are sequentially added into hydroxy acrylic resin or hydroxy polyurethane resin, and the mixture is dispersed at 1500rpm for 20 minutes to obtain a component A.
TABLE 1 formulation of component A
| Formulation of | Monk (monk's syndrome) |
| Bayhydrol A2470 | 70 |
| BYK 028 | 0.5 |
| BYK 346 | 0.5 |
| BUTYL CELLOSOLVE | 2 |
| RHEOVIS PU 1291 | 1 |
| Deionized water | 26 |
| Total weight of | 100 |
The 50g A component and the modified polyisocyanate of the present invention or the comparative modified polyisocyanate were mixed in a molar ratio of isocyanate groups and alcoholic hydroxyl groups of 1.5: 1 and stirred manually using a wooden stick for 30 seconds to obtain aqueous two-component coating compositions of examples and comparative examples.
Water dispersibility test method
7.5g of water were added to the aqueous two-component coating composition, stirred well by hand and filtered through a 100 mesh sieve, and the residue on the sieve was visually observed. The less residue on the screen means the better dispersion of the modified polyisocyanate in the resin system. According to the fact that the residues on the filter screen are from large to small, the dispersibility of the modified polyisocyanate in a resin system is evaluated as 1-3 minutes, and 1 is evaluated that a large amount of residues exist on the filter screen; 2, the filter screen has more residues; the 3 point is that almost no residue is left on the filter screen, the 1 point is the worst, and the 3 point is the best.
Gloss and haze test conditions
Adding 7.5g of water into the aqueous two-component coating composition, stirring uniformly by hand, filtering with a 100-mesh filter screen, coating the filtered coating on a black plastic plate with a wet film thickness of 120 microns, drying in air to obtain a coating, and testing the gloss and haze data of the coating.
Judging and qualified standards of gloss and haze: the 60 DEG gloss is more than 80, the haze value is less than 100, the higher the 60 DEG gloss value is, the higher the gloss of the coating is, and the higher the haze value is, the poorer the transparency of the coating is.
Table 2 shows the formulations and test results for the aqueous two-component coating compositions of examples 1 to 5 and comparative examples 1 to 6.
TABLE 2 formulation and test results for aqueous two-component coating compositions
The aqueous two-component coating compositions of examples 1 to 5 have good dispersibility and form coatings having good gloss and transparency. The aqueous two-component coating compositions of comparative examples 1 to 5 formed coatings with good gloss and transparency, but the aqueous two-component coating compositions had poor dispersibility, i.e., the coating had poor hand stir performance, which was disadvantageous for construction. The aqueous two-component coating composition of comparative example 6 has poor dispersibility and forms a coating having poor gloss and transparency.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (31)
1. A modified polyisocyanate comprising an iminooxadiazinedione structure and an isocyanurate structure in a weight ratio of not less than 1: 5; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate; the modified polyisocyanate is obtainable from a reaction comprising:
a. at least one sulfamic acid;
b. at least one polyisocyanate;
c. at least one tertiary amine; and
d. optionally a polyether alcohol containing ethylene oxide groups.
2. The modified polyisocyanate of claim 1, wherein the modified polyisocyanate has a molecular weight distribution of 1.2 to 2.0.
3. Modified polyisocyanate according to claim 1 or 2, characterized in that the modified polyisocyanate has a weight ratio of iminooxadiazinedione structures to isocyanurate structures of 1: 5 to 1: 1, most preferably 1: 5 to 1: 2.
4. Modified polyisocyanate according to any one of claims 1 to 3, characterized in that the total amount of molecules having a number average molecular weight of more than 2700g/mol is 4.1 to 20 wt. -%, further preferably 4.1 to 16 wt. -%, most preferably 4.1 to 11 wt. -%, relative to the total weight of the modified polyisocyanate.
5. Modified polyisocyanate according to any one of claims 1 to 4, characterized in that the modified polyisocyanate has a molecular weight distribution of 1.3 to 1.7, most preferably 1.3 to 1.6.
6. Modified polyisocyanate according to any one of claims 1 to 5, characterized in that the modified polyisocyanate has a sulphonate group in an amount of 0.1 to 7 wt. -%, relative to the total weight of the modified polyisocyanate.
7. The modified polyisocyanate of any one of claims 1 to 6, wherein the modified polyisocyanate has a viscosity of greater than 2250mPa.s and not more than 30000mPa.s, most preferably 2300mPa.s to 15000mPa.s, as measured without the modified polyisocyanate comprising a solvent.
8. Modified polyisocyanate according to any one of claims 1 to 7, characterized in that the modified polyisocyanate has a number average molecular weight of 700g/mol to 1500g/mol, further preferably 750g/mol to 1200g/mol, still more preferably 750g/mol to 1000g/mol, most preferably 750g/mol to 900g/mol, according to gel permeation chromatography and DIN 55672-1: 2016-03, and is obtained by taking polystyrene as a standard substance and taking tetrahydrofuran as an eluent for testing.
9. Modified polyisocyanate according to any one of claims 1 to 8, characterized in that the modified polyisocyanate has an isocyanate group content of from 7% to 23% by weight, further preferably from 19% to 22% by weight, most preferably from 19.5% to 22% by weight, relative to the total weight of the modified polyisocyanate.
10. The modified polyisocyanate of any one of claims 1 to 9, wherein component a) sulfamic acid is according to formula I:
wherein the content of the first and second substances,
R1and R2Each independently is hydrogen, a substituted or unsubstituted and/or heteroatom-containing aliphatic group having 1 to 18 carbon atoms, a substituted or unsubstituted and/or heteroatom-containing cycloaliphatic group having 3 to 18 carbon atoms, a substituted or unsubstituted and/or heteroatom-containing aromatic group having 1 to 18 carbon atoms; r1And R2Reacting to form an alicyclic group having 3 to 8 carbon atoms or a heterocyclic group having 3 to 8 carbon atoms substituted with an oxygen atom or a nitrogen atom; r3Is a linear or branched aliphatic group having 2 to 8 carbon atoms.
11. The modified polyisocyanate of any one of claims 1 to 10, wherein component a) R of the sulfamic acid3Is a linear or branched aliphatic group having 2 to 4 carbon atoms, further preferably a linear or branched aliphatic group having 2 to 3 carbon atoms, most preferably a linear or branched aliphatic group having 3 carbon atoms.
12. The modified polyisocyanate of any one of claims 1 to 11, wherein the component a) sulfamic acid is one or more of the following: 3-cyclohexylaminopropane-1-sulfonic acid, 4-cyclohexylamino-1-butanesulfonic acid and 2-cyclohexylaminoethane-1-sulfonic acid, further preferably one or more of the following: 3-cyclohexylaminopropane-1-sulfonic acid and 4-cyclohexylamino-1-butanesulfonic acid, with 3-cyclohexylaminopropane-1-sulfonic acid being most preferred.
13. Modified polyisocyanate according to any one of claims 1 to 12, characterized in that the amount of sulfamic acid of component a) is from 1.5% to 3.5% by weight, preferably from 2% to 3% by weight, most preferably from 2.2% to 2.9% by weight, relative to the total weight of components a) and b).
14. The modified polyisocyanate of any one of claims 1 to 13, wherein the amount of the sulfonate group of the sulfamic acid of component a) is from 0.1 to 7% by weight, relative to the total weight of the modified polyisocyanate.
15. The modified polyisocyanate according to any one of claims 1 to 14, characterized in that the polyisocyanate of component b) comprises iminooxadiazinedione structures and isocyanurate structures in a weight ratio of more than 1: 5, preferably more than 1: 5 and not more than 1: 1, further preferably from 1: 4 to 1: 1, most preferably from 1: 4 to 1: 2.
16. The modified polyisocyanate of any one of claims 1 to 15, wherein the polyisocyanate of component b) is one or more of the following: aliphatic and cycloaliphatic polyisocyanates, most preferably one or more of the following: a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure.
17. The modified polyisocyanate according to any one of claims 1 to 16, characterized in that the ethylene oxide group content of the polyether alcohol comprising an ethylene oxide group is from 0 to 17% by weight, preferably from 0 to 13% by weight, most preferably from 0 to 5% by weight, relative to the total weight of the components of the reaction.
18. The modified polyisocyanate of any one of claims 1 to 17, wherein the modified polyisocyanate is obtained by a reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid;
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure; and
c. a tertiary amine;
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 1, the number average molecular weight of the modified polyisocyanate is 700g/mol-1500g/mol, and the molecular weight distribution is 1.2-2.0; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1 to 22% by weight, relative to the total weight of the modified polyisocyanate.
19. The modified polyisocyanate of any one of claims 1 to 18, wherein the modified polyisocyanate is obtained by a reaction comprising:
3-cyclohexylaminopropane-1-sulfonic acid and/or 4-cyclohexylamino-1-butanesulfonic acid in an amount of from 0.28% to 22% by weight, relative to the total weight of the components a) and b);
b. a derivative of hexamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure and/or a derivative of pentamethylene diisocyanate having an isocyanurate structure and an iminooxadiazinedione structure, the weight ratio of the iminooxadiazinedione structure and the isocyanurate structure of component b) being greater than 1: 5 and not greater than 1: 1, further preferably from 1: 4 to 1: 1, most preferably from 1: 4 to 1: 2;
c. n, N-dimethylcyclohexylamine in a molar equivalent ratio of from 0.3 to 1.9, based on the sulfonate groups of component a);
the weight ratio of the iminooxadiazinedione structure to the isocyanurate structure of the modified polyisocyanate is 1: 5-1: 2, the number average molecular weight of the modified polyisocyanate is 750g/mol-900g/mol, and the molecular weight distribution is 1.3-1.6; the total amount of molecules having a number average molecular weight of more than 2700g/mol in the modified polyisocyanate is 4.1% to 15% by weight, relative to the total weight of the modified polyisocyanate.
20. Use of the modified polyisocyanates according to any of claims 1 to 19 as starting components in the preparation of polyurethanes.
21. Use of the modified polyisocyanates according to any of claims 1 to 19 as crosslinking components for water-soluble or water-dispersible coatings, adhesives or sealants.
22. Use of the modified polyisocyanates according to any of claims 1 to 19 as starting components for preparing sealant-blocked polyisocyanates.
23. A coating, adhesive or sealant comprising the modified polyisocyanate of any one of claims 1 to 19.
24. A substrate coated with the coating composition, adhesive or sealant of claim 23.
25. Use of the modified polyisocyanate of any one of claims 1 to 19 to improve the hand-rub of a coating, adhesive or sealant.
26. An aqueous two-component coating composition comprising: at least one aqueous hydroxyl resin dispersion, at least one modified polyisocyanate according to any one of claims 1 to 19, optionally auxiliaries and optionally additives.
27. A method of preparing an aqueous two-component coating composition comprising the steps of: mixing an aqueous hydroxyl resin dispersion, and optionally additives, in any desired manner to give a mixture, mixing the modified polyisocyanate according to any one of claims 1 to 19 with said mixture, and manually stirring to give said aqueous two-component coating composition.
28. A product comprising a substrate and a coating formed by applying the aqueous two-component coating composition according to claim 26 to the substrate.
29. The product of claim 28, wherein the substrate is wood, metal, alloy, or inorganic material.
30. The article of claim 28, wherein the article is furniture.
31. A method of manufacturing a product by applying the aqueous two-component coating composition according to claim 26 to a substrate followed by curing and drying.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011069929.1A CN114316211A (en) | 2020-09-30 | 2020-09-30 | Modified polyisocyanates |
| EP21786390.1A EP4222184A1 (en) | 2020-09-30 | 2021-09-29 | A modified polyisocyanate |
| PCT/EP2021/076827 WO2022069561A1 (en) | 2020-09-30 | 2021-09-29 | A modified polyisocyanate |
| CN202180066330.9A CN116209692A (en) | 2020-09-30 | 2021-09-29 | Modified polyisocyanates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011069929.1A CN114316211A (en) | 2020-09-30 | 2020-09-30 | Modified polyisocyanates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114316211A true CN114316211A (en) | 2022-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011069929.1A Pending CN114316211A (en) | 2020-09-30 | 2020-09-30 | Modified polyisocyanates |
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| Country | Link |
|---|---|
| CN (1) | CN114316211A (en) |
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2020
- 2020-09-30 CN CN202011069929.1A patent/CN114316211A/en active Pending
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