WO1998006768A9 - Compositions polymeres sulfonees a base d'eau - Google Patents
Compositions polymeres sulfonees a base d'eauInfo
- Publication number
- WO1998006768A9 WO1998006768A9 PCT/US1997/014386 US9714386W WO9806768A9 WO 1998006768 A9 WO1998006768 A9 WO 1998006768A9 US 9714386 W US9714386 W US 9714386W WO 9806768 A9 WO9806768 A9 WO 9806768A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfonated
- water
- polyurethane
- polymer
- dispersion
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 229920000642 polymer Polymers 0.000 title claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 65
- 239000006185 dispersion Substances 0.000 claims abstract description 56
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 41
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 24
- -1 alkali metal salts Chemical class 0.000 claims description 21
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 18
- 229920001228 Polyisocyanate Polymers 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920005906 polyester polyol Polymers 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 230000001681 protective Effects 0.000 claims description 9
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive Effects 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 4
- 239000011152 fibreglass Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000000977 initiatory Effects 0.000 claims 1
- 239000002987 primer (paints) Substances 0.000 claims 1
- 229920000126 Latex Polymers 0.000 abstract description 19
- 239000004816 latex Substances 0.000 abstract description 19
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 91
- 239000008367 deionised water Substances 0.000 description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 28
- 239000007787 solid Substances 0.000 description 28
- 229920005862 polyol Polymers 0.000 description 20
- 150000003077 polyols Chemical class 0.000 description 20
- 229920003226 polyurethane urea Polymers 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- 239000003638 reducing agent Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 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 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 230000000875 corresponding Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tBuOOH Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 7
- 229920000122 Acrylonitrile butadiene styrene Polymers 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N N-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000006196 drop Substances 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N Acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N DETA Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M Rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-Butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920001451 Polypropylene glycol Polymers 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N TMPTA Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- DUYAAUVXQSMXQP-UHFFFAOYSA-N Thioacetic acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- BHBPJIPGXGQMTE-UHFFFAOYSA-N ethane-1,2-diol;2-methylprop-2-enoic acid Chemical compound OCCO.CC(=C)C(O)=O.CC(=C)C(O)=O BHBPJIPGXGQMTE-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HCTAATFCJCAWHB-UHFFFAOYSA-L 1,2,3,4,5,6-hexamethylbenzene;dicyanate Chemical compound [O-]C#N.[O-]C#N.CC1=C(C)C(C)=C(C)C(C)=C1C HCTAATFCJCAWHB-UHFFFAOYSA-L 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N 2-methylpropanenitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N Allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- 240000000218 Cannabis sativa Species 0.000 description 1
- 210000001736 Capillaries Anatomy 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N Citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N Crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- 241000287227 Fringillidae Species 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N Isoniazid Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N Mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L Sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003111 delayed Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymerization Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000003889 eye drop Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N hexane-1,2,6-triol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XKORCTIIRYKLLG-ARJAWSKDSA-N methyl (Z)-3-aminobut-2-enoate Chemical compound COC(=O)\C=C(\C)N XKORCTIIRYKLLG-ARJAWSKDSA-N 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Definitions
- This invention relates to water-based polymers, specifically to a method for the preparation of water-based sulfonated polymer compositions having enhanced mechanical and adhesion properties.
- U.S. Pat. No. 5,334,690 (Hoechst Aktiengesellschaft) discloses water- based sulfonated polyurethane-urea polymers which can be combined with and are in general compatible with other aqueous polymer dispersions.
- U.S. Pat. No. 4,888,383 discloses a process wherein water-based polyurethane-urea modified acrylic polymers are prepared by reacting amine and/or hydrazide functional polyacrylic polymers with isocyanate terminated polyurethane prepolymers.
- the present invention discloses water-based sulfonated polymer compositions comprising:
- At least one isocyanate-terminated polyurethane prepolymer comprising; a) at least one polyisocyanate; and b) at least one sulfonated polyester polyol wherein the sulfonate groups are present in the form of alkali metal salts;
- an aqueous polyvinyl dispersion comprising; a) at least one ethylenically unsaturated monomer; and optionally, b) at least one free radically reactive protective colloid comprising active hydrogen atoms.
- the sulfonated polymer compositions have enhanced mechanical and adhesion properties and show stability at pH values greater than about 2.0. It is surmised that some of these unique properties can be attributed to the development of interpenetrating polymer networks and the sulfonate character located in the polyol segment of the polyurethane polymer.
- inventive compositions are useful as adhesives, binders, coatings and primers on any substrate including paper, wood, metals, concrete, glass, cloth and synthetic polymers, and are useful in applications including fiber grass sizing, woodworking, automotive, film laminating and in the manufacture of shoes.
- the present invention discloses a method for the preparation of sulfonated polymer compositions wherein isocyanate terminated polyurethane prepolymers are dispersed in aqueous polyvinyl dispersions which may contain primary amines, secondary amines, primary hydroxyl groups, secondary hydroxyl groups and formamide groups.
- the method comprising: A) forming a water dispersible isocyanate-terminated polyurethane prepolymer by reacting;
- the present invention discloses a water based sulfonated polymer composition and a method of making the same by seed emulsion polymerization.
- the composition comprises the reaction product of: a) at least one sulfonated polyurethane dispersion; b) at least one aqueous ethylenically unsaturated monomer pre- emulsion comprising at least one ethylenically unsaturated monomer; and c) an initiator.
- the method of preparing the same comprises the steps of: a) forming an aqueous pre-emulsion comprising at least one ethylenically unsaturated monomer pre-emulsion comprising at least one ethylenically unsaturated monomer and optionally at least one surfactant; and b) reacting said aqueous pre-emulsion with at least one sulfonated polyurethane dispersion optionally in the presence of an initiator solution and optionally in the presence of a reducer solution.
- the present invention discloses a polyurethane/polyvinyl hybrid latex and a method of making the same by seed emulsion polymerization.
- the hybrid latex comprises the seed emulsion polymerization reaction of: a) at least one sulfonated polyurethane dispersion, the polyurethane serving as a seed; b) at least one aqueous ethylenically unsaturated monomer pre- emulsion comprising at least one ethylenically unsaturated monomer; and c) at least one free radical initiator.
- Figure 1 is a graph showing the seed polyurethane particle size distribution (dotted line) as a function of the final hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Example 6.
- Figure 2 is a graph showing the seed polyurethane particle size distribution (dotted line) as a function of the final hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Example 7.
- polyvinyl dispersions include dispersions of addition polymerization products of ethylencially unsaturated monomers including, but not limited to (meth)acrylate monomers.
- polyurethane refers in the present application to a polymer containing more than one urethane group and is intended to include polyurethanes containing urea groups as well (polyurethane-ureas).
- interpenetrating polymer network is defined as a crosslinked and/or semi crosslinked system comprising at least two dissimilar or different polymers. IPNs are further described in the "Handbook of Adhesives", Irving Skeist, 3rd edition, chapter 1, page 18, VanNostrand, NY, 1990.
- hybrid denotes a polymer comprised of two or more dissimilar polymers. The dissimilar polymers may or may not be covalent linked.
- aqueous polyvinyl dispersions which may contain active hydrogen atoms such as primary amines, secondary amines, primary hydroxyl groups and secondary hydroxyl groups
- the isocyanate terminated polyurethane prepolymer dispersions interact with the aqueous polyvinyl dispersions to form IPNs and crosslinked networks.
- the frequency of such interactions can be influenced by the quantity of isocyanate and active hydrogen atoms present in the respective polymer dispersions. It is possible to increase the crosslink density using a structured aqueous polyvinyl dispersion wherein active hydrogen atoms are distributed on the surface of the particle.
- a structured particle can be generated when ethylenically unsaturated monomers, containing active hydrogen atoms, are added at the end of the free radical emulsion polymerization process. It is believed that such a particle morphology improves the collision frequency of the isocyanate/active hydrogen atom reaction to increase the composition's crosslink density.
- the dispersed particles can contain a complex mixture of polymers consisting of sulfonated polyurethane-urea polymers, polyvinyl polymers and sulfonated polyurethane-vinyl polymers.
- the complex particle mixtures can be formed when substantially dissimilar or substantially different polymers diffuse and interact or crosslink with adjacent particles.
- Such diffusion processes may generate particles having polymers within the particle that are different when compare with polymers on the surface of the particle.
- examples include particles having substantially polyvinyl based polymers on the surface of predominantly polyurethane-urea based particles or substantially polyurethane-urea based polymers on the surface of predominantly polyvinyl based particles.
- Such surface layers may be continuous or non-continuous and can vary in thickness. If a particle's surface layer has a substantial thickness, as well as being continuous, then the particle approaches a core-shell type structure.
- the isocyanate-terminated polyurethane prepolymers of the present invention may be formed using monoisocyanates and polyisocyanates.
- the isocyanates may be linear aliphatic, cyclic aliphatic, aromatic and mixtures thereof. Examples of commercially available polyisocyanates include Vestanat® IPDI which is isophorone diisocyanate from HULS America Inc.
- TMXDT® which is tetramethylxylene diisocyanate from Cyanamid (Wayne, NJ)
- Luxate® HM which is hexamethylene diisocyanate from Olin Corporation (Stamford, CN)
- diphenylmethane diisocyanate from Upjohn Polymer Chemicals (Kalamazoo, MI)
- Desmodur® W which is dicyclohexylmethane-4,4'-diisocyanate from Bayer Corporation (Pittsburgh, PA) and toluene diisocyanate (TDI).
- the preferred diisocyanates are hexamethylene diisocyanate, isophorone diisocyanate and their mixtures.
- polyisocyanates which have an isocyanate content greater than 2.1 may be used.
- modified polyisocyanates which are prepared from hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate may also be used.
- Said polyisocyanates can have functionalities including urethanes, uretdiones, isocyanurates, biurets and mixtures thereof.
- the sulfonated polyester polyol component used in the preparation of the isocyanate-terminated polyurethane prepolymer can have hydroxyl numbers, as determined by ASTM designation E-222-67 (Method B), in a range from about 20 to about 140, and preferably from about 40 to about 110.
- the polyols may be formed with components such as diacids, diols, sulfonate diols and sulfonate diacids. Such polyols and their preparation are further described in U.S. Pat. No. 5,334,690, incorporated herein by reference.
- the preferred sulfonated polyester polyols are based on 5- sulfoisophthalic acid monosodium salt, adipic acid and 1,6-hexanediol and/or diethylene glycol. It is believed that the sulfonate character, which is present in the polyol segment, enhances the polymer's dispersibility and stability at reduced pH.
- non-sulfonated polymeric diols may be used in combination with the sulfonated polyester polyols.
- Such polyols may have hydroxyl numbers in a range from about 20 to about 140, and preferably from about 40 to about 110.
- the non- sulfonated polymeric polyols may include polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacetal polyols, polyacrylate polyols, polycaprolactone polyols, polyesteramide polyols, polythioether polyols, and mixtures thereof.
- Alkylene diols may also be used in the preparation of the isocyanate - terminated prepolymers.
- the alkylene diols may have hydroxyl numbers in a range from about 130 to about 1250, and preferably from about 950 to about 1250.
- the preferred alkylene diols include 1 ,4-butanediol, 1,6-hexanediol and 2-methyl-l,3-propanediol and may be present in the isocyanate terminated polyurethane prepolymer in a range from about 0.1% by weight to about 10.0% by weight, and preferably from about 0.5% by weight to about 5.0% by weight, based on 100 parts of total prepolymer solids.
- Higher functional polyols may be used in the preparation of the polyurethane-urea polymers. Suitable examples include glycerol, trimethylolpropane, 1,2,4-butane triol, 1,2,6-hexane triol and mixtures thereof.
- the preferred higher functional polyol is trimethylolpropane.
- Said polyols may be present in a range from about 0.1% by weight to about 1.0% by weight, and preferably from about 0.3% by weight to about 0.7% by weight, based on 100 parts of total isocyanate-terminated polyurethane prepolymer solids.
- dihydroxy carboxylic acids may be used when preparing the isocyanate-terminated polyurethane prepolymer.
- a preferred dihydroxy carboxylic acid is dimethylolpropionic acid.
- the dihydroxy carboxylic acid component may be present in a range from about 0.05% by weight to about 1.0% by weight, and preferably from about 0.2% by weight to about 0.5% by weight, based on 100 parts total polyurethane prepolymer solids.
- Neutralization of the dihydroxy carboxylic acid groups can be accomplished with compounds such as alkali metal hydroxides, organic tertiary amines, ammonia and mixtures thereof.
- Preferred neutralizing agents are sodium hydroxide and triethylamine.
- Conversion of the acid groups to ionic groups (salts) can be accomplished before, or at the same time, that, the isocyanate terminated polyurethane prepolymer has been dispersed in the polyvinyl dispersion mixture.
- the isocyanate-terminated polyurethane prepolymer is prepared by reacting a stoichiometric excess of polyisocyanate with said polyol components.
- the reactants are in such proportions that the resulting percent isocyanate may be in a range from about 1.0% by weight to about 10.0% by weight, and preferably from about 2.0% by weight to about 5.0% by weight, based on 100 parts total of isocyanate terminated polyurethane prepolymer solids.
- the prepolymers may be processed at temperatures in a range from about 30°C to about 110°C, and preferably from about 65°C to about 85°C. Additionally, small quantities of catalysts may be used to accelerate the hydroxy/isocyanate reaction.
- the catalysts can be present in a range from about 0.05% by weight to about 2.0% by weight, and preferably from about 0.13% by weight to about 0.15% by weight, based on 100 parts total isocyanate-terminated polyurethane prepolymer solids.
- An example includes MetacureTM T-12 which is an organic tin compound from Air Products and Chemicals, Inc. (Allentown, PA).
- the ethylenically unsaturated monomers can include monounsaturated monomers, polyunsaturated monomers and mixtures thereof. Examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propylacrylate, iso-propyl acrylate, methyl methacrylate, butyl methacrylate, vinyl acetate, vinyl propionate, vinyl ethers, ethylenically unsaturated fumerates, ethylenically unsaturated maleates, styrene, acrylonitrile, acrylamides, butanediol diacrylate, hexanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
- Ethylenically unsaturated monomers containing anionic and/or ionic groups can be used.
- examples of such monomers include acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, mesaconic acid, maleic acid, citraconic acid and/or their corresponding ionic groups.
- Said monomers may be in a range from about 0.1% by weight to about 25.0% by weight, and preferably from about 0.1% by weight to about 10.0% by weight, based on 100 parts total composition solids.
- Ethylenically unsaturated monomers containing active hydrogen atoms may also be used.
- active hydrogen atoms refers to hydrogens which display activity according to the Zerewitinoff test as described by Kohlerin, J Am. Chem. Soc, 49, 3181 (1927). Examples include hydroxy ethyl acrylate, allyl alcohol, allyl amine, N- methylol acrylamide, mono-acrylic acid esters of glycols, itaconic acid and methyl-3- aminocrotonate. Amine and hydroxyl functional protective colloids may be used to prepare the aqueous polyvinyl dispersion of the present invention.
- Suitable examples include the water dispersible polyvinyl alcohol-copoly(vinyl amine) polymers described in EP 0599245 assigned to Air Products and Chemicals, Inc. (Allentown, PA).
- Such protective colloids may have an amine content in a range from about 0.5 meq. amine/gram to about 3.5 meq. amine/gram, and preferably from about 1.0 meq. amine/gram to about 3.0 meq. amine/gram.
- the number average molecular weight may be in a range from about 10,000 grams/mol. to about 350,000 grams/mol., and preferably from about 30,000 grams/mol. to about 250,000 grams/mol.
- Said colloids can be present in a range from about 0.1% by weight to about 20.0% by weight, and preferably from about 0.5% by weight to about 5.0% by weight, based on 100 parts total polyacrylic solids. It is assumed grafting reactions occur during the emulsion polymerization process. The graft copolymerization process is further described in "Polyvinyl Alcohol Developments", edited by CA. Finch, John Wiley & Sons, New York, 1992, pp. 449-453.
- Specialty monomers may also be incorporated into the aqueous polyvinyl dispersions and include the amino organo-silane coupling agents described in U.S. Pat. No. 4,745,028 (PPG) and U.S. Pat. No. 5,236,982, (Owens-Corning), the imidazolidinone functional wet adhesion monomers described in U.S. Pat. No. 5,496,907, (H.B. Fuller Co., St. Paul, MN) and the VinamerD EF monomer which is N- ethenylformamide from Air Products Chemicals, Inc. (Allentown, PA).
- the bound formamide group may be hydrolyzed to a primary amine using catalysts such as bases or acids including sodium hydroxide, hydrochloric acid and sulfuric acid.
- catalysts such as bases or acids including sodium hydroxide, hydrochloric acid and sulfuric acid.
- the resulting amine functional polyvinyl can then be used as a reactive component in the process of the present invention.
- the aqueous polyvinyls can be formed using materials and free radical polymerization processes known in the art.
- the free radical initiators used in the addition polymerization process, may be water soluble, oil soluble or mixtures thereof. Examples include hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, 2,2-azobis (2,4-dimethylpentanenitrile), 2,2-azobis (2- methylpropanenitrile) and mixtures such as t-butylhydroperoxide, Fe'EDTA and isoascorbic acid.
- Said initiators may be present in amounts from about 0.05% by weight to about 1.5% by weight, and preferably from about 0.1% by weight to about 0.5% by weight, based on 100 parts total solids.
- oxidizing catalysts may be used independently or in combination with reducing agents such as sodium formaldehyde- sulfoxylate, ferrous salts, sodium dithionite, sodium hydrogen sulfite, sodium sulfite and sodium thiosulfate.
- the redox catalysts may be present in amounts from about 0.05% by weight to about 1.5% by weight, preferably from about 0.1% by weight to about 0.5% by weight, based on 100 parts total solids.
- the ethylenically unsaturated monomers are polymerized using free radical polymerization techniques known in the art.
- the free radical initiators can be added all at once, slowly over time or as a partial initial charge with the remainder being added slowly over time.
- Free radical polymerization may be conducted at temperatures in a range from about 5°C to about 85°C, and preferably from about 25°C to about 80°C.
- the water-based sulfonated polymer compositions of the present invention are formed using a method wherein isocyanate-terminated polyurethane prepolymers are dispersed in an aqueous polyvinyl dispersion which may contain primary amines, secondary amines, primary hydroxyl groups,, secondary hydroxyl groups and formamide groups. It is also possible to disperse the isocyanate-terminated polyurethane prepolymer in water and then immediately blend with the aqueous polyvinyl dispersion. Optionally, the aqueous polyvinyl dispersion may be added to a neat or water dispersed isocyanate-terminated polyurethane prepolymer.
- the dissimilar polymers are suitably combined at temperature in a range from about 25°C to about 95°C, preferably from about 45°C to about 75°C.
- the polymer components may be blended using an equivalence ratio of amine active hydrogen to isocyanate in a range from about 1 : 10 to about 10:5, and preferably from about 1:5 to about 5:1.
- water soluble compounds containing primary and/or secondary amines may be reacted with the polymer mixture of the invention. Suitable examples include monoethanolamine, ethylenediamine, diethylene triamine and ammonia.
- the water-based sulfonated polymer compositions may have viscosities in a range from about 10 mPa.s to about 1,000 mPa.s, and preferably from about 10 mPa.s to about 500 mPa.s.
- the particle size distribution may be monomodal or multimodal and generally will have a mean diameter in a range from about 0.01 microns to about 2.0 microns.
- the water-based sulfonated polymer compositions may have a solids content in the range from about 20% by weight to about 70% by weight, and preferably from about 35% by weight to about 55% by weight of the total composition.
- the dried sulfonated polymer compositions may have single or multiple glass transition (Tg.) temperatures in a range from about -100°C to about +200°C.
- the present invention is also directed to a water based sulfonated polymer composition which may be used, inter alia, for fiberglass sizing and a method for making the same.
- the water-based sulfonated polyurethane polyvinyl hybrid latex of the present invention comprises the reaction product of at least one sulfonated polyurethane dispersion, at least one aqueous ethylenically unsaturated monomer pre-emulsion comprising at least one ethylenically unsaturated monomer and at least one free radical initiator, such as those disclosed above.
- the present invention is also directed to a water-based sulfonated polymer composition
- a water-based sulfonated polymer composition comprising particles, the particles comprising a core and a surface wherein the core and surface comprise substantially different polymers, the core comprising at least one polymer selected from the group consisting of sulfonated polyurethane polymers and sulfonated polyurethane-urea polymers and mixtures thereof, the surface comprising predominantly polyvinyl polymers.
- the composition may be formed from the free radical seed emulsion polymerization of at least one ethylencially unsaturated monomer in the presence of a sulfonated polyurethane or polyurethane-urea dispersion, the polyurethane serving as a seed.
- Sulfonated polyurethane dispersions such as those been disclosed in U.S.
- the aqueous ethylenically unsaturated monomer will preferably be chosen from among acrylate monomers, (meth)acrylate monomers, (meth)acrylic monomers, vinyl monomers, allylic monomers, acrylamide monomers or mixtures thereof.
- acrylate monomers include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-propylacrylate, iso- propyl acrylate, butyl methacrylate, hexanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate and mixtures thereof.
- the emulsion comprising the monomer will comprise methyl methacrylate, n-butyl acrylate, hydroxy ethyl methacrylate and mixtures thereof.
- any of the ethylenically unsaturated monomers mentioned above such as ethylenically unsaturated monomers comprising anionic and/or ionic groups, or ethylenically unsaturated monomers containing active hydrogen atoms may be used as well.
- a suitable surfactant such as Pluronic L64 (manufactured by BASF) or a combination of surfactants may be used in preparing the pre-emulsion
- the ratio of sulfonated polyurethane solids to polyvinyl solids is from about 9:1 to about 1:9.
- the ratio is from about 4:1 to about 1 :4 and most preferably, the ratio is from about 4:1 to about 2:1.
- the present invention is also directed to a water-based sulfonated polyurethane polyvinyl hybrid latex comprising polyurethane polyvinyl particles wherein the average particle size is at least 200 nm.
- the water-based sulfonated polymer compositions formed via the seed emulsion polymerization are characterized by high lap shear strengths of at least about 350 psi.
- the present invention is also directed to a method for preparing the above-mentioned polyurethane polyvinyl latex hybrid.
- the method comprises the steps of forming an aqueous pre-emulsion comprising at least one ethylenically unsaturated monomer, the pre-emulsion comprising at least one acrylate and optionally a surfactant and reacting the aqueous pre-emulsion with at least one sulfonated polyurethane dispersion in the presence of at least one free radically initiator.
- the aqueous polyvinyl pre-emulsion may be formed by dispersing ethylenically unsaturated monomers in water, with a surfactant and agitating the mixture.
- the polyurethane polyvinyl latex dispersion is then formed by adding an initiator solution such as t-butyl hydrogen peroxide, a reducer solution such as hydrosulfite and the pre-emulsion to a polyurethane dispersion.
- the initiator may already be present in the pre-emulsion or in the polyurethane dispersion.
- the mixture is allowed to react over a period of time at a temperature between 50°C and 100-C, preferably at 65°C.
- the characteristics of the water-based sulfonated polymer compositions may be modified by the addition of compounds including surfactants, defoaming agents, coalescing aids, fungicides, bactericides, polyfunctional crosslinking agents, plasticizers, thickening agents, fillers, pigments, reactive pigments, dispersing agents for the pigments, colors, perfume-like materials, UV stabilizers, sequestering agents, waxes, oils, fire retardant agents and organic solvents.
- Such materials may be introduced at any stage of the production process.
- the polymer dispersions were cast to generated dried films having a thickness in a range from about 20 mils, to about 40 mils.
- Type V dogbones were cut with a Dewes Gumbs Die and conditioned at least 24 hours in an environment having 50% relative humidity at 23°C. The samples were run using ASTMD-638 at a crosshead speed of 5.0 cm./min.
- the polymer dispersions were coated on steel, acrylonitrile-butadienestyrene (ABS) and glass then dried 24 hours. Like substrates were mated using hand pressure then heat activated at 70°C for 30 minutes. The samples, which has a bond area of 0.5 x 1.0 inches, were run using ASTM-D-1002 at a crosshead speed of 1.27 cm/min. Peel Strength:
- Peel strength was measured as follows. A precut sheet (10.5 x 12.75 inch) of 10 mil thick clear, pressed, polished PVC was cleaned with isopropyl alcohol and placed on a glass or aluminum plate containing a small amount of isopropyl alcohol. Excess isopropyl alcohol was removed to produce a good seal. The exposed PVC surface was wiped with isopropyl alcohol. An adhesive film, dispensed from a film applicator set to 5 mils, was cast over the PVC sheet, according to the method of ASTM specification D323-87. The adhesive was allowed to dry at ambient temperature. A second sheet of PVC, cleaned similarly to the first sheet, was placed over the first coated PVC sheet. The PVC adhesive sandwich was cut into 1 inch strips and allowed to dry over 2 hours.
- the strips were placed into a heat sealer with the uncoated PVC in contact with the upper platen, the upper platen having been preheated to 190°F and with a pressure setting of 50 psi. Following a 30 second dwell time, the temperature at the bond line was 160°F. A minimum of 6 bonds per strip were heat sealed with a total bond area of 1 inch by 7 inches with 1.5 inches of no bond on both ends.
- the bonds were allowed to age at ambient temperature for 1 to 2 hours and 1 week prior to testing. Testing was performed on a Thwing Albert Intellect 500 with a cross head speed of 12 inches per minute, a 1 inch prepeel and 3 inches of recorded peel.
- the sample was coated on glass and allowed to dry overnight. The bond area was 0.5x1.0 in .
- the lap shear sample was maintained at 160°F for 30 minutes. Lap shear strength was then measured using ASTM D- 1002 with a crosshead speed of 0.5 in/minute. The measurement was made under an environment of 50% relative humidity at a temperature of 23 °C.
- Example 1 This example describes the preparation of a water-based sulfonated polyurethane-vinyl polymer composition. The composition and its properties are compared to its corresponding polymer components.
- Compound 1A is an aqueous polyvinyl dispersion prepared with a reactive emulsifying agent which is polyvinyl alcohol/polyvinylamine copolymer
- PVOH/PVAM 6% vinyl amine, medium M.W.
- Acetic acid 350.00
- reactor charge (1) To a reactor equipped with an agitator, thermometer, condenser and nitrogen purge was added reactor charge (1). The mixture was heated to 65°C and agitated for 30 minutes. While maintaining the reaction temperature at 65°C, the pre- emulsion (2) and surfactant feed (3) was added over a 3 hour period. The initiator feed (4) and reducer feed (5) were added over a 3.5 hour period. Once all the materials were added, the dispersion was heated an additional 30 minutes. The polymer had a solids content of 33.2% and a pH of 2.65.
- Compound IB is a water-based sulfonated polyurethane-urea polymer.
- a reactor was charged with 4.5 grams (0.099 hydroxyl equivalence) 2 - methyl- 1,3 -propanediol and 95.4 grams (0.093 hydroxyl equivalents) molten Rucoflex®.
- XS-5570-55 which is a sulfonated polyol from Ruco Polymer Corporation based on 5- sulfoisophthalic acid monosodium salt (4% by weight), adipic acid and diethylene glycol.
- Compound IC is a water-based sulfonated polyurethane-vinyl polymer.
- the dispersed prepolymer was charged with 341.5 grams of an amine and hydroxyl functional polyvinyl dispersion (Compound 1 A). The mixture was agitated and heated to 65°C for 2 hours.
- the water- based sulfonated polyurethane-vinyl polymer had a solids content of 40.2% and a pH of 6.4.
- the data shows the sulfonated polyurethane-vinyl polymer (Compound IC) has enhanced mechanical properties compared to the blend of Compound 1A and IB.
- the data also shows Compound IC has enhanced adhesion properties compared to Compound 1 A, Compound IB and their 50/50 blend, thus showing the utility of the invention.
- This example describes the preparation of a water-based sulfonated polyurethane-vinyl polymer using vinyl acetate.
- the inventive polymer properties are compared to its corresponding polymer components.
- Compound 2A is an aqueous polyvinyl acetate dispersion using a reactive emulsifying agent, which is polyvinyl alcohol-polyvinylamine copolymer (PVOH- PVAM), from Air Products & Chemicals, Inc. (Allentown, PA).
- a reactive emulsifying agent which is polyvinyl alcohol-polyvinylamine copolymer (PVOH- PVAM), from Air Products & Chemicals, Inc. (Allentown, PA).
- the polymer was prepared as described in Example 1 (Compound 1 A) with the exception that the pre-emulsion contained 265.0 grams vinyl acetate, 35.0 grams n-butyl acrylate, 3.9 grams methacrylic acid and 0.10 grams thiolacetic acid.
- the resulting polymer dispersion had a solid content of 33.6% and a pH of 2.5.
- Compound 2B is a sulfonated polyurethane prepolymer.
- the polymer was prepared exactly as described in Example 1 (Compound IB).
- Compound 2C is a water-based sulfonated polyurethane-vinyl acetate polymer.
- the data shows the sulfonated polyurethane-vinyl acetate polymer (Compound 2C) has enhanced mechanical properties compared to the blend of Compounds 2 A and 2B.
- the data also shows Compound 2C has enhanced adhesion properties compared to Compound 2 A and Compound 2B thus showing the utility of the invention.
- This example describes the preparation of a water-based sulfonated polyurethane-vinyl polymer wherein the amine functional polyvinyl dispersion is formed using Vinamer EF monomer which is N-ethenylformamide from Air Products & Chemicals, Inc. (Allentown, PA).
- Compound 3 A is an amine functional polyvinyl dispersion using N- ethenylformamide.
- the pre-emulsion (2) was prepared using the following procedure. The water, surfactant, defoamer and initiator were combined and agitated for 15 minutes. The monomers were added to this mixture over a 30 minute period, using agitation, to form a milky white pre-emulsion.
- Compound 3B is a water-based sulfonated polyurethane-vinyl polymer.
- Example 4 describes the preparation of water-based polymer compositions wherein isocyanate-terminated sulfonated polyurethane prepolymers are dispersed in hydroxy functional water-based polyacrylic dispersions.
- Compound 4A is a hydroxyl functional polyacrylic dispersion wherein the hydroxyl groups are within the latex particle.
- Compound 4B is a hydroxyl functional polyacrylic dispersion wherein a portion of the hydroxyl groups are distributed on the surface of the particle.
- Compound 4D is a water-based sulfonated polyurethane-urea polymer. 139.86 grams of the prepolymer (80°C) described as Compound 4C was charged with 629.3 grams de-ionized water (65°C) and stirred for 2 hours keeping the temperature below 65°C. Compound 4E
- Compound 4E is of a water-based sulfonated polyurethane-acrylic polymer composition.
- Compound 4F was prepared as similarly described as Compound 4E with the exception that 312.2 grams of the hydroxyl functional polyacrylic dispersion described as Compound 4B was used.
- the polymer composition had a solids content of 40% and a pH of 6.5.
- Example 5 This example describes the preparation of a water-based sulfonated polyurethane-urea/polyvinyl polymer and its properties compared to its corresponding polymer components.
- Compound 5 A describes the preparation of a polyvinyl dispersion which is free of active hydrogen atoms.
- Compound 5B is a water-based sulfonated polyurethane-urea polymer. To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents)
- Compound 5C is a water-based sulfonated polyurethane-urea/polyvinyl dispersion. To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents)
- the resulting isocyanate- terminated polyurethane prepolymer/polyvinyl dispersion was charged with a solution containing 2.88 grams ethylene diamine, 1.09 grams diethylene triamine and 20 grams de-ionized water.
- the resulting water-based sulfonated polyurethane-urea/polyvinyl polymer had a solids content of 35% and a pH of 9.0.
- the data shows the inventive polymer (Compound 5C) has increased shear strength compared to Compound 5 A, Compound 5B and the 50/50 blend of Compound 5 A and 5B showing the utility of the invention.
- Examples 6 and 7 relate to the formation of water based sulfonated polymer compositions in which a polyurethane dispersion is used as a seed to polymerize (meth)acrylic monomers.
- the resulting water based sulfonated polymer composition may be used for fiberglass sizing.
- acrylic denotes acrylate, methacrylic acid, and acrylamide.
- Example 6 describes the preparation of a water based sulfonated polymer composition by seed emulsion polymerization and its properties compared to the blend of its corresponding polymer components.
- Compound 6A is a polyacrylate pre-emulsion.
- Pluronic L64 (a surfactant, BASF) 9.08
- Reactor charge (1) was added to a kettle with an agitator and mixed for 10 minutes at a temperature of 25°C.
- Monomer mixture (2) was then added over a period of
- Compound 6B is a polyurethane dispersion for use in the preparation of the inventive compositions.
- Reactor charge (1) was added to a jacketed clean reaction kettle equipped with agitator, thermometer, condenser and nitrogen purge and mixed well. 332.3 Grams of NP-4062-M (a polyurethane dispersion, H.B. Fuller Company) was added to the mixture. The reactor, under nitrogen purge, was agitated and the temperature raised to 65°C.
- Compound 6C Compound 6C is a water based sulfonated polymer composition prepared by seed emulsion polymerization.
- the polyacrylate pre-emulsion (Compound 6 A), an initiator solution containing 1.95 grams of t-butyl hydrogen peroxide (Akzo) and 19.5 grams of deionized water, a reducer solution containing 0.91 grams of hydrosulfite AWC (Henkel) and 19.5 grams of deionized water, were fed to a jacketed clean reaction kettle equipped with agitator, thermometer, condenser and nitrogen purge containing the polyurethane dispersion mixture (Compound 6B). Following completion of the feeds, the mixture was held at constant temperature for another hour to allow the full conversion of monomers. The reactor was then cooled to ambient temperature and the resulting latex filtered through 200 mesh filter. A stable latex with 45% solids, pH 7.35 and viscosity of 316 cps was obtained.
- Additional compounds were prepared similarly to compound 6C varying the amount of compound 6B resulting in a water based sulfonated polymer composition with different polyurethane /polyacrylate (PU/PA) ratios.
- Compound 6C, and similarly prepared compounds with different polyurethane/polyacrylic ratios, and blends of compounds 6 A and 6B, (absent the initiator and reducer solutions) were tested for tensile strength and elongation, peel strength (using a clear and a white PVC sheet as substrates) and lap shear strength. The results are provided in Tables 6-9. Note that the polyurethane to polyacrylate ratio is based on solids content of the polyurethane and the polyacrylate.
- a PU/PA ratio of 75/25 indicates that there are 3 parts polyurethane solids for every part of polyacrylate solids.
- the "hybrid" referred to in Table 9 is prepared as in Compound 6C with a PU/PA ratio of 25/75.
- the blend in Table 9 has a PU/PA ratio of 25/75.
- Example 6 Another water based sulfonated polymer composition was prepared in the manner of Example 6C except that the polyurethane dispersion NP-4062 used to prepare compound 6B was replaced by NP- 4073 (a sulfonated polyurethane dispersion, H.B. Fuller Company).
- NP-4062 used to prepare compound 6B was replaced by NP- 4073 (a sulfonated polyurethane dispersion, H.B. Fuller Company).
- Figures 1 and 2 present the seed polyurethane particle size distribution (dotted line) as a function of the final hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Examples 6 and 7. Both figures demonstrate that no new population of acrylic particles was generated, implying that a polyurethane-core-polyacrylic-shell hybrid structure was formed.
- the unique hybrid morphology of the water based sulfonated polymer composition latex in this disclosure leads to superior physical properties compared to the corresponding blend or common alloy.
Abstract
Méthode de préparation de compositions polymères sulfonées selon laquelle des prépolymères dispersables dans l'eau se terminant par l'isocyanate entrent en réaction en présence de dispersions aqueuses de polyvinyle pouvant contenir des atomes d'hydrogène actif. En outre, l'invention concerne un latex hybride de polyvinyle de polyuréthanne sulfonée à base d'eau, où la polyuréthanne sulfonée est utilisée en tant que germe lors de la polymérisation de monomères non saturés d'éthylène, ainsi qu'une méthode de fabrication de ladite composition. Les compositions inventées peuvent développer un alliage IPN ou former des structures du type noyau-enveloppe et se distinguent par leurs propriétés mécaniques et leur adhérence améliorées.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU40693/97A AU4069397A (en) | 1996-08-13 | 1997-08-13 | Water-based sulfonated polymer compositions |
EP97938336A EP0918807A1 (fr) | 1996-08-13 | 1997-08-13 | Compositions polymeres sulfonees a base d'eau |
BR9711064A BR9711064A (pt) | 1996-08-13 | 1997-08-13 | Composi-{es de polimero sulfonado a base de gua e m-todos para prepara-Æo de composi-{es de polimero sulfonado a base de gua |
JP51005598A JP2002514233A (ja) | 1996-08-13 | 1997-08-13 | 水系スルホン化ポリマー組成物 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/689,752 US5807919A (en) | 1996-08-13 | 1996-08-13 | Water-based sulfonated polymer compositions |
US08/689,752 | 1996-08-13 | ||
US08/909,578 | 1997-08-12 | ||
US08/909,578 US6031045A (en) | 1996-08-13 | 1997-08-12 | Water-based sulfonated polymer compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998006768A1 WO1998006768A1 (fr) | 1998-02-19 |
WO1998006768A9 true WO1998006768A9 (fr) | 1998-07-23 |
Family
ID=27104479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/014386 WO1998006768A1 (fr) | 1996-08-13 | 1997-08-13 | Compositions polymeres sulfonees a base d'eau |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0918807A1 (fr) |
JP (1) | JP2002514233A (fr) |
CN (1) | CN1227576A (fr) |
BR (1) | BR9711064A (fr) |
CA (1) | CA2259364A1 (fr) |
WO (1) | WO1998006768A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007502350A (ja) | 2003-08-13 | 2007-02-08 | ヴァルスパー ソーシング,インク. | 水系ポリウレタン‐ポリエチレン系組成物 |
JP2005113128A (ja) * | 2003-09-16 | 2005-04-28 | Jsr Corp | 粘着剤組成物とその製造方法および粘着性物品 |
US20090088846A1 (en) | 2007-04-17 | 2009-04-02 | David Myung | Hydrogel arthroplasty device |
US20080075685A1 (en) * | 2006-09-22 | 2008-03-27 | Steven Michael Baxter | Polymer compositions containing polyurethanes |
US20120209396A1 (en) | 2008-07-07 | 2012-08-16 | David Myung | Orthopedic implants having gradient polymer alloys |
JP5752035B2 (ja) * | 2008-07-07 | 2015-07-22 | バイオミメディカ インコーポレイテッド | 疎水性ポリマーに由来する親水性相互貫入ポリマーネットワーク |
CN101638559B (zh) * | 2008-07-29 | 2013-02-13 | 上海奇想青晨新材料科技股份有限公司 | 一种改良水性复膜胶及其制备方法 |
JP5722773B2 (ja) | 2008-08-05 | 2015-05-27 | バイオミメディカ インコーポレイテッド | ポリウレタングラフト化ヒドロゲル |
CA2808528A1 (fr) | 2010-08-27 | 2012-03-01 | Biomimedica, Inc. | Reseaux de polymere hydrophobe et hydrophile interpenetrant derives de polymeres hydrophobes et procedes de preparation de ceux-ci |
AU2012319183A1 (en) | 2011-10-03 | 2014-05-22 | Biomimedica, Inc. | Polymeric adhesive for anchoring compliant materials to another surface |
KR20140113655A (ko) | 2011-11-21 | 2014-09-24 | 바이오미메디카, 인코포레이티드 | 정형외과적 임플란트를 뼈에 앵커링하기 위한 시스템, 장치, 및 방법 |
JP6106515B2 (ja) * | 2012-05-09 | 2017-04-05 | 第一工業製薬株式会社 | ガラス繊維用集束剤 |
JP5830444B2 (ja) | 2012-07-02 | 2015-12-09 | 信越ポリマー株式会社 | 導電性高分子組成物、該組成物より得られる帯電防止膜が設けられた被覆品、及び前記組成物を用いたパターン形成方法。 |
US11077228B2 (en) | 2015-08-10 | 2021-08-03 | Hyalex Orthopaedics, Inc. | Interpenetrating polymer networks |
US10869950B2 (en) | 2018-07-17 | 2020-12-22 | Hyalex Orthopaedics, Inc. | Ionic polymer compositions |
FR3109583B1 (fr) * | 2020-04-28 | 2022-07-29 | Arkema France | Dispersion aqueuse de poly(ester-uréthane) ou de poly(ester-urée-uréthane) |
US11801143B2 (en) | 2021-07-01 | 2023-10-31 | Hyalex Orthopaedics, Inc. | Multi-layered biomimetic osteochondral implants and methods of using thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56157476A (en) * | 1980-05-09 | 1981-12-04 | Toyobo Co Ltd | Aqueous treating agent |
US4318833A (en) * | 1980-05-16 | 1982-03-09 | Inmont Corporation | Water reducible coating compositions of acrylic-urethane polymers |
US5134035A (en) * | 1990-06-25 | 1992-07-28 | Minnesota Mining And Manufacturing Company | Magnetic recording medium containing a polyurethane copolymer with a free radically polymerized polymer segment grafted to the polyurethane through a sulfur atom |
DE4137429A1 (de) * | 1991-11-14 | 1993-05-19 | Bayer Ag | Waessrige bindemittelkombination, ein verfahren zu ihrer herstellung und ihre verwendung |
US5834554A (en) * | 1996-03-05 | 1998-11-10 | H. B. Fuller Licensing & Financing, Inc. | Laminating adhesives for flexible packaging |
-
1997
- 1997-08-13 BR BR9711064A patent/BR9711064A/pt not_active Application Discontinuation
- 1997-08-13 EP EP97938336A patent/EP0918807A1/fr not_active Withdrawn
- 1997-08-13 CA CA002259364A patent/CA2259364A1/fr not_active Abandoned
- 1997-08-13 CN CN97197245A patent/CN1227576A/zh active Pending
- 1997-08-13 WO PCT/US1997/014386 patent/WO1998006768A1/fr not_active Application Discontinuation
- 1997-08-13 JP JP51005598A patent/JP2002514233A/ja active Pending
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