CN111574704A - 用芳基醚烷氧基化物嵌段共聚物封端的环氧烷聚合物 - Google Patents
用芳基醚烷氧基化物嵌段共聚物封端的环氧烷聚合物 Download PDFInfo
- Publication number
- CN111574704A CN111574704A CN202010079026.5A CN202010079026A CN111574704A CN 111574704 A CN111574704 A CN 111574704A CN 202010079026 A CN202010079026 A CN 202010079026A CN 111574704 A CN111574704 A CN 111574704A
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- CN
- China
- Prior art keywords
- phenyl
- naphthyl
- alkylene oxide
- hydrophobically modified
- polymer
- 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.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims description 50
- 125000002947 alkylene group Chemical group 0.000 title claims description 22
- 229920001400 block copolymer Polymers 0.000 title description 7
- 150000008378 aryl ethers Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 52
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- -1 o-methylphenyl Chemical group 0.000 claims description 16
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- PBJZAYSKNIIHMZ-UHFFFAOYSA-N ethyl carbamate;oxirane Chemical class C1CO1.CCOC(N)=O PBJZAYSKNIIHMZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 26
- 239000006254 rheological additive Substances 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical group C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 11
- 239000002562 thickening agent Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000001542 size-exclusion chromatography Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 239000000174 gluconic acid Substances 0.000 description 6
- 235000012208 gluconic acid Nutrition 0.000 description 6
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 5
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QFXBYZKQOKCTQA-UHFFFAOYSA-N (carbamoylamino) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ONC(N)=O QFXBYZKQOKCTQA-UHFFFAOYSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- WGFZZGXKRATULP-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)aniline Chemical compound NC1=CC=CC=C1OCC1OC1 WGFZZGXKRATULP-UHFFFAOYSA-N 0.000 description 2
- RXBOCDZLKBPILN-UHFFFAOYSA-N 2-propylheptyl prop-2-enoate Chemical compound CCCCCC(CCC)COC(=O)C=C RXBOCDZLKBPILN-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 2
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- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical class O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- FMFWSIARXFCACS-UHFFFAOYSA-N 2-[bis(2-ethylhexyl)amino]ethanol Chemical compound CCCCC(CC)CN(CCO)CC(CC)CCCC FMFWSIARXFCACS-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
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- PFYWPQMAWCYNGW-UHFFFAOYSA-M [6-(dimethylamino)-9-(2-methoxycarbonylphenyl)xanthen-3-ylidene]-dimethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.COC(=O)C1=CC=CC=C1C1=C2C=CC(=[N+](C)C)C=C2OC2=CC(N(C)C)=CC=C21 PFYWPQMAWCYNGW-UHFFFAOYSA-M 0.000 description 1
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- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
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Abstract
本发明涉及一种化合物，其包含具有由结构I表示的疏水性片段的疏水改性聚(氧化烯‑氨基甲酸酯)：
其中Ar1、Ar2；R1、m和n定义于本文中。本发明化合物提供含有疏水改性聚(氧化烯‑氨基甲酸酯)流变改性剂，更确切地说HEUR流变改性剂的油漆在着色后的粘度稳定性。
Description
背景技术
本发明涉及用芳基醚烷氧基化物嵌段共聚物封端的环氧烷聚合物，其适用于改进着色涂料配制物的粘度保持力。
因为疏水改性环氧烷聚合物，更确切地说疏水改性环氧乙烷氨基甲酸酯聚合物(HEUR)提供良好流动性和耐垂挂性的组合，所以其为用于油漆的优选流变改性剂。然而，标准HEUR长期存在的缺点为，在添加着色剂时，HEUR增稠油漆的粘度典型地显著降低。这种非所期望的效果对于中度和深度着色油漆而言尤其麻烦。粘度损失使得油漆太“稀”，并且确切地说，耐垂挂性变得不可接受地低，引起其在墙面上流淌和滴落，和/或非常差的辊点画图案。因此，找到在添加着色剂后具有改进的粘度保持力的含HEUR的油漆配制物将为着色油漆领域中的一项进步。
发明内容
本发明通过提供一种包含疏水改性环氧烷聚合物的化合物解决了所属领域中的需要，所述疏水改性环氧烷聚合物具有由结构I表示的疏水性片段：
其中虚线表示所述片段与所述疏水改性环氧烷聚合物的连接点；Ar1为未被取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；或被1到3个C1-C6烷基或烷氧基取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；并且Ar2为苯基、苯基-OCH2CH2-、苯基-(OCH2CH2)y-、苄基、萘基、萘基-CH2-、萘基-OCH2CH2-或萘基-(OCH2CH2)y-，其中Ar2的苯基或萘基部分未被取代或被1到3个C1-C6烷基取代；其中y为2到10；每一R1独立地是H或C1-C6烷基；X是O或NR2，其中R2是H、C1-C6烷基、苯基或苄基；m是1到20；并且n是0到100。本发明化合物通过提供含有疏水改性环氧烷流变改性剂的油漆在着色后的粘度稳定性来解决所属领域中的需要。
具体实施方式
本发明是包含疏水改性环氧烷聚合物的化合物，所述疏水改性环氧烷聚合物具有由结构I表示的疏水性片段：
其中虚线表示所述片段与所述疏水改性环氧烷聚合物的连接点；Ar1为未被取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；或被1到3个C1-C6烷基或烷氧基取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；并且Ar2为苯基、苯基-OCH2CH2-、苯基-(OCH2CH2)y-、苄基、萘基、萘基-CH2-、萘基-OCH2CH2-或萘基-(OCH2CH2)y-，其中Ar2的苯基或萘基部分未被取代或被1到3个C1-C6烷基取代；其中y为2到10；每一R1独立地是H或C1-C6烷基；X是O或NR2，其中R2是H、C1-C6烷基、苯基或苄基；m是1到20；并且n是0到100。
如本文中所用，术语“环氧烷聚合物”是指水溶性聚环氧乙烷聚合物，以及水溶性聚环氧乙烷/聚环氧丙烷和聚环氧乙烷/聚环氧丁烷共聚物。优选地，环氧烷聚合物为环氧烷氨基甲酸酯聚合物，更优选地为环氧乙烷氨基甲酸酯聚合物。
如本文所用，疏水改性环氧烷氨基甲酸酯聚合物是指聚乙烯、聚丙烯或聚环氧丁烷氨基甲酸酯聚合物，优选地为经具有结构I的疏水性片段改性的聚环氧乙烷氨基甲酸酯聚合物(HEUR)。
具有结构I的片段由封端剂产生，所述封端剂通过在反应性条件下使以下接触在一起而方便地制备：a)二异氰酸酯；b)水溶性聚亚烷基二醇；和c)为由结构II表示的化合物的封端剂：
合适的二异氰酸酯的实例包括1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)、2,2,4-三甲基-1,6-二异氰酸酯基己烷、1,10-十亚甲基二异氰酸酯、4,4′-亚甲基双(异氰酸酯基环己烷)(H12-MDI)、2,4′-亚甲基双(异氰酸酯基环己烷)、1,4-亚环己基二异氰酸酯、1-异氰酸酯基-3-异氰酸酯基甲基-3,5,5-三甲基环己烷(IPDI)、间亚苯基二异氰酸酯和对亚苯基二异氰酸酯、2,6-甲苯二异氰酸酯和2,4-甲苯二异氰酸酯(TDI)、二甲苯二异氰酸酯、4-氯-1,3-亚苯基二异氰酸酯、4,4′-亚甲基二苯基二异氰酸酯(MDI)、1,5-亚萘基二异氰酸酯和1,5-四氢亚萘基二异氰酸酯。市售二异氰酸酯的实例是Desmodur W环脂肪族二异氰酸酯(DesW)和Desmodur H(HDI)。
水溶性聚亚烷基二醇是指水溶性聚环氧乙烷、水溶性聚环氧乙烷/聚环氧丙烷共聚物和水溶性聚环氧乙烷/聚环氧丁烷共聚物。优选的水溶性聚亚烷基氧化物是聚乙二醇，特别是重均分子量在范围600到12,000道尔顿(Dalton)的聚乙二醇。合适的聚乙二醇的实例为可以CARBOWAXTM8000聚乙二醇购得的PEG 8000(PEG-8000，陶氏化学公司(The DowChemical Company)(“陶氏”)或密歇根州米德兰(Midland,MI)的陶氏附属公司的商标)。
在反应条件下使二异氰酸酯、聚亚烷基二醇和具有结构II的封端剂接触，形成疏水改性环氧烷氨基甲酸酯聚合物。优选地，通过如本文所描述的尺寸排阻色谱法(SEC)测定，疏水改性环氧烷氨基甲酸酯聚合物的重均分子量(Mw)在2000、更优选地4000道尔顿到优选地50,000、更优选地25,000道尔顿的范围内。本发明的片段的优选子类实例由以下结构表示：
其中R1'为H或CH3；且R2'为CH3或苄基。
优选地，Ar1为苯基-OCH2-或邻-甲基苯基-OCH2-；优选地，当X＝O时，Ar2为苯基、苄基、苯基-OCH2CH2-或邻-甲基苯基；优选地，当X＝NR2时，Ar2为苄基或苯基；且R2为苄基、甲基或乙基。优选地，m在1、更优选地2到10、更优选地6的范围内；并且n在0到40的范围内。优选地，每一R1独立地为H、甲基或乙基；更优选地为H或甲基；最优选地，每一R1为H。优选地，X为O、N-CH3、N-苯基或N-苄基。
优选地，如在下文实例部分所描述，通过基质辅助激光解吸/电离质谱(matrix-assisted laser desorption/ionization-mass spectrometry，MALDI-MS)测定，具有结构I的片段(和具有结构II的化合物)的数均分子量(Mn)在500g/mol、更优选750g/mol到10,000，更优选到2500g/mol，并且最优选地到1500g/mol的范围内。
式II化合物可方便地通过以下步骤来制备：首先，在催化量的合适的碱(如KOH)的存在下，在足以制备芳基烷氧基醚低聚物中间物的条件下，使芳基醇或芳基胺与芳基环氧化物或芳基缩水甘油醚接触，接着，优选地使中间物与环氧烷(如环氧乙烷)在足以形成所要式II化合物的条件下接触。优选地，芳基醇为苯酚、甲酚或苯氧乙醇或其组合；芳基胺优选地为N-甲基苄胺或二苄胺或其组合；并且芳基烷氧基醚优选地为苯基缩水甘油醚或甲苯基缩水甘油醚或其组合。
有利地将本发明化合物与各种其它添加剂一起溶解于水中以制备水性增稠剂组合物。按水性增稠剂组合物的总重量计，水性增稠剂组合物包含1重量％，并且更优选地5重量％到60重量％，并且更优选地到40重量％的增稠剂固体。可在水性增稠剂组合物中包括其它添加剂以抑制水性增稠剂组合物的粘度。此类其它添加剂包括可混溶水的溶剂，如丙二醇和二乙二醇丁基醚。其它添加剂的实例包括环糊精和各种非离子和阴离子表面活性剂。优选非离子表面活性剂的实例包括
C6-C18醇乙氧基化物、月桂醇乙氧基化物、格尔伯特醇乙氧基化物(guerbetalcohol ethoxylates)和蓖麻油乙氧基化物。在TERGITOLTM商标(陶氏化学公司或其附属公司的商标)下的表面活性剂也是合适的。合适的阴离子表面活性剂的实例包括C6-C18醇硫酸盐、磺酸盐、磺基丁二酸盐、磷酸盐以及其乙氧基化物，包括月桂基硫酸钠、2-乙基己基硫酸钠、十二烷基苯磺酸钠和二辛基磺基丁二酸钠。
对于其中X＝NR2的本发明化合物，优选地将足够的酸添加到相应水性增稠剂组合物中以将其pH调节到2.1到6.0范围内。可将pH降低到此范围的任何酸化合物均为合适的。优选酸的实例包括葡糖酸、磷酸、盐酸、硫酸、乳酸和聚(丙烯酸)。
本发明化合物适用作着色涂料配制物中的流变改性剂。在另一个实施例中，本发明为一种包含水性分散体的组合物，所述水性分散体具有以下：a)按组合物的重量计，10重量％到60重量％的聚合物颗粒；b)和按组合物的重量计，0.05重量％到2重量％的具有疏水性片段的疏水改性环氧烷氨基甲酸酯聚合物，所述疏水性片段具有结构I。
聚合物颗粒(即胶乳)的水分散体优选地是包含丙烯酸酯或甲基丙烯酸酯单体或乙烯基酯单体或其组合的结构单元的聚合物颗粒的分散体。
指明单体的术语“结构单元”是指聚合之后单体的残余物。例如，甲基丙烯酸甲酯的结构单元如所示：
其中虚线代表结构单元与聚合物主链的连接点。
优选地，聚合物颗粒包含至少30重量％，更优选地至少50重量％的丙烯酸酯和甲基丙烯酸酯单体的结构单元，或优选地包含至少30重量％，更优选地至少50重量％的乙烯基酯单体的结构单元。合适的丙烯酸酯和甲基丙烯酸酯单体的实例包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸脲基酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯和丙烯酸2-丙基庚酯。丙烯酸酯和甲基丙烯酸酯单体的优选组合包括甲基丙烯酸甲酯和选自由丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸脲基酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组中的一或多种单体。更优选的丙烯酸单体的组合包括甲基丙烯酸甲酯和丙烯酸丁酯；甲基丙烯酸甲酯和丙烯酸2-乙基己酯；和甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸乙酯，其中甲基丙烯酸甲酯和丙烯酸丁酯的组合是最优选的。基于乙烯基酯的单体的实例包括乙酸乙烯酯和叔碳酸乙烯酯。基于乙烯基酯的共聚物的实例是乙酸乙烯酯-乙烯(VAE)。
聚合物颗粒还可以包括其它单体，如苯乙烯、甲基丙烯酸乙酰乙酰氧基乙酯(acetoacetoxyethyl methacrylate)、丙烯腈、丙烯酰胺，和2-丙烯酰氨基-2-甲基丙磺酸的结构单元。另外，聚合物颗粒优选地包含0.2重量％、更优选地0.5重量％、最优选地1重量％到优选地5重量％、更优选到地3重量％的烯系不饱和羧酸单体(如丙烯酸、甲基丙烯酸或衣康酸)的结构单元。
本发明的第二方面的组合物可以足够浓度与着色剂接触以赋予所要颜色。如本文所用，“着色剂”是指有色颜料的液体分散体。着色剂的浓度一般为油漆和着色剂总体积的5到20体积％。有色颜料的实例包括酞菁蓝、酞菁绿、单芳基黄、二芳基黄、苯并咪唑酮黄、杂环黄、DAN橙、喹吖啶酮品红、喹吖啶酮紫、有机红(包括金属化偶氮红和非金属化偶氮红)、炭黑、灯黑、氧化铁黑、氧化铁黄、氧化铁棕和氧化铁红。
在另一方面，组合物包含小于15PVC的TiO2或BaSO4颗粒；又在另一方面，组合物包含小于10PVC的TiO2和BaSO4颗粒。对于深色基底配制物，TiO2和BaSO4颗粒的PVC<1。PVC由以下公式定义：
其中粘合剂固体是指聚合物颗粒的水性分散体将颜料和增量剂颗粒粘合在一起的聚合物贡献。
组合物可进一步包括以下材料中的任一种或全部：粘合剂、分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂和不透明聚合物。
实例
分子量测量
用于测量中间物实例的分子量的MALDI-MS Mn方法
在配备有氮激光器(λ＝337nm)的Bruker Daltonics ultraflex MALDI-TOF质谱仪上获得MALDI质谱。在MALDI实验中，将20mg的2,5-二羟基苯甲酸溶解在1mL的THF中以作为MALDI基质。将于MeOH中的样品溶液与基质溶液以1:20的比例预混合。为了促进样品混合物中的物质的离子化，将NaI加入到样品/基质混合物中。然后将0.3μl的混合物样品置于样品板上并风干以进行MALDI-MS分析。在分析中选择反射器(reflectron)模式以提高质谱的解析度。
用于测量HEUR的Mw的SEC方法
通过将1-2mg聚合物/克100mM乙酸铵溶解在甲醇中来制备样品。通过在室温下在机械振荡器上振荡过夜将样品置于溶液中。使用0.45μm PTFE过滤器过滤样品溶液。
在Waters Acquity APC系统上进行分离，所述系统由等度泵、脱气机、进样器、柱加热炉以及在40℃下运行的UV和RI检测器组成。使用Empower软件版本3(马萨诸塞州米尔福德沃特世(Waters，Milford，MA))进行系统控制、数据采集和数据处理。使用由两个装有购自沃特世(马萨诸塞州米尔福德)的BEH二醇颗粒(分别孔径标记为BEH
和BEH
粒度为1.7和2.5μm)的水APC柱(150×4.6mm ID)组成的APC柱组，以0.5mL/min的速度在100mM含乙酸铵的甲醇(来自Fisher的Optima级)中进行SEC分离。注射20μL的样品用于APC分离。
从较窄的聚环氧乙烷(PEO)标准获得3阶十二点校准曲线。
中间物实例1-制备苯基缩水甘油醚聚合物
将苯酚(102.44克，1.09摩尔)、甲苯(337.83克)和KOH薄片(8.12g，90％纯)装入装备有温控加热套、加料漏斗、回流/蒸馏头和顶置式搅拌器的2L圆底烧瓶中。将溶液在N2下加热以蒸出一部分甲苯(110g)。然后在110℃到120℃下将苯基缩水甘油醚(490.78g，3.27摩尔)历时4小时加入所得的浓缩溶液中。将混合物再搅拌2小时，并使烧瓶冷却。用乙酸处理产物，并且在真空中去除溶剂，形成如通过MALDI-MS所测量，Mn为780g/mol的中间物分布，且所述中间物包括具有以下结构的化合物：
中间物实例2-制备苯基缩水甘油醚乙氧基化物嵌段共聚物
将苯酚(62.94g，0.67摩尔)、甲苯(341.34g)和KOH薄片(4.75g，90％纯)装入装备有温控加热套、加料漏斗、回流/蒸馏头和顶置式搅拌器的2L圆底烧瓶中。将溶液在N2下加热以蒸出一部分甲苯(82.81g)。然后在110℃到120℃下历时4小时将苯基缩水甘油醚(502.18g，3.34摩尔)加入到所得浓缩溶液中，并且再搅拌混合物2小时。将一部分所得溶液(374.9g)装入锥形底部2L帕尔反应器(Parr reactor)中。将反应器密封，检查压力，用N2吹扫，然后加热到120℃。以1到2g/min的速率加入环氧乙烷(289.3g)。将混合物在120℃下保持1小时，然后冷却到60℃，之后倒出产物(650.6g)。反应产物用乙酸(1.07g)处理，且在真空中去除溶剂以形成如通过MALDI-MS所测量，Mn为1840g/mol的中间物分布，且所述中间物包括具有以下结构的化合物：
中间物实例3-制备苯基缩水甘油醚乙氧基化物嵌段共聚物
将DOWANOLTMEPh(陶氏化学公司或其附属公司的商标，179.95g)和90％氢氧化钾(3.36g)装入锥形底部2L帕尔反应器中并且密封反应器，检查压力，用氮气吹扫，然后加热到100℃。然后使用Gilson HPLC泵以4mL/min的速率将苯基缩水甘油醚(587g)添加到反应器中。反应通过在此添加期间产生的热量而显而易见。在完成添加苯基缩水甘油醚后，将混合物在100℃下保持过夜。将反应混合物温度增加到120℃，并且然后以1.5g/min的速率将环氧乙烷(286.9g)添加到反应器中。在完成添加环氧乙烷后，将反应混合物在120℃下保持过夜。将反应混合物冷却到80℃后，吹扫反应器顶部空间。用乙酸(3.18g)处理反应混合物，然后从反应器倒出，形成形成如通过MALDI-MS所测量，Mn＝968g/mol的中间物分布，且所述中间物包括具有以下结构的化合物：
中间物实例4-制备氨基苯基缩水甘油醚乙氧基化物嵌段共聚物
将N-甲基苄胺(157.8g)和90％氢氧化钾(3.36g)装入向锥形底部2L帕尔反应器中。将反应器密封，检查压力，并且用氮气吹扫，然后加热到100℃。然后使用Gilson HPLC泵以4mL/min的速率将苯基缩水甘油醚(587g)添加到反应器中。在完成添加苯基缩水甘油醚后，将混合物在100℃下保持过夜。将反应混合物温度增加到120℃，此时以1.5g/min的速率将环氧乙烷(286.9g)添加到反应器中。在完成添加环氧乙烷后，将反应混合物在120℃下保持过夜。将反应混合物冷却到80℃后，吹扫反应器顶部空间。反应混合物用乙酸(3.18g)处理，且接着从反应器倒出，形成如通过MALDI-MS所测量，Mn＝878g/mol的中间物分布，且所述中间物包括具有以下结构的化合物：
中间物实例5-制备氨基苯基缩水甘油醚乙氧基化物嵌段共聚物
将二苄胺(256.9g)和90％氢氧化钾(3.36g)装入锥形底部2L帕尔反应器中。密封反应器，检查压力，并用氮气吹扫，然后加热至100℃。然后使用Gilson HPLC泵以4mL/min的速率将苯基缩水甘油醚(587g)添加到反应器中。在完成添加苯基缩水甘油醚后，将混合物在100℃下保持过夜。将反应混合物温度增加到120℃，此时以1.5g/min的速率将环氧乙烷(286.9g)添加到反应器中。在完成添加环氧乙烷后，将反应混合物在120℃下保持过夜。将反应混合物冷却到80℃后，吹扫反应器顶部空间。反应混合物用乙酸(3.18g)处理，且接着从反应器倒出，形成形成如通过MALDI-MS所测量，Mn＝1009g/mol的中间物分布，且所述中间物包括具有以下结构的化合物：
实例1：制备聚芳基烷氧基化HEUR
将PEG 8000(75.0g)在甲苯(150g)中的混合物加热到回流，并通过共沸蒸馏干燥2小时。然后将反应器冷却到90℃并且将Desmodur W环脂肪族二异氰酸酯(Des W，6.64g)添加到反应器中搅拌5分钟。然后添加二月桂酸二丁锡(0.21g)，并且在90℃下搅拌反应混合物1小时。将反应混合物冷却到80℃并且将中间物实例1(30.56g)中制备的聚芳基烷氧基化物添加到反应器中并且在80℃下搅拌所得混合物1小时。在真空中去除溶剂，得到白色固体产物。通过如上文所述的SEC测量发现Mw为17,298。在添加到涂料配制物中之前，制备含有20重量％HEUR聚合物和16重量％丁基卡必醇的水性溶液。
实例2：制备聚芳基烷氧基化HEUR
将PEG 8000(50.0g)在甲苯(150g)中的混合物加热到回流，并通过共沸蒸馏干燥2小时。然后将反应器冷却到90℃并且将Des W(4.43g)添加到反应器中搅拌5分钟。然后添加二月桂酸二丁锡(0.21g)，并且在90℃下搅拌反应混合物1小时。然后将反应混合物冷却到80℃，并且将中间物实例2(47.19g)中制备的聚芳基烷氧基化物添加到反应器中，并且在80℃下搅拌所得混合物1小时。在真空中去除溶剂，得到白色固体产物。通过如上文所述的SEC测量发现Mw为17,903。在添加到涂料配制物中之前，制备含有20重量％HEUR聚合物和16重量％丁基卡必醇的水性溶液。
实例3-制备聚芳基烷氧基化HEUR
将CARBOWAXTMPEG8000(75.0g)在甲苯(150g)中的混合物加热到回流，并通过共沸蒸馏干燥2小时。然后将反应器冷却到90℃并且将Des W(7.18g)添加到反应器中搅拌5分钟。然后添加二月桂酸二丁锡(0.21g)，并且在90℃下搅拌反应混合物1小时。然后将反应混合物冷却到80℃，并且将中间物实例3(38.59g)中制备的聚芳基烷氧基化物添加到反应器中，并且在80℃下搅拌所得混合物1小时。在真空中去除溶剂，得到白色固体产物。通过如上文所述的SEC测量发现Mw为17,609。含有20重量％聚合物和16重量％丁基卡必醇的水性溶液的布鲁克费尔德粘度(Brookfield viscosity)为1420cP(3号转子，6rpm)。还可通过用表面活性剂代替丁基卡必醇而使聚合物在无有机溶剂的情况下溶解。举例来说，含有20重量％聚合物和20重量％TERGITOLTM15-S-9表面活性剂(15-S-9)的水性溶液的布鲁克费尔德粘度为2800cP(3号转子，6rpm)。
实例4-制备氨基聚芳基烷氧基化HEUR
在真空中在间歇熔融反应器中，将CARBOWAXTM8000聚乙二醇(PEG；1200g)加热到110℃维持2小时。然后将丁基化羟基甲苯(BHT，0.132g)和Desmodur W(114.9g)添加到反应器中并且搅拌反应混合物5分钟。然后将辛酸铋(28％Bi，3.0g)添加到反应器中，并且在110℃下搅拌所得混合物10分钟。然后将中间物实例4(500.09g)添加到反应器中并且在110℃下搅拌所得混合物10分钟。将所得熔融聚合物从反应器中移出并冷却。水性增稠剂组合物通过将聚合物溶于含有20重量％聚合物固体、2重量％葡糖酸和78重量％水的具有葡糖酸的水中来制备。
表1展示在对具有疏水性片段的HEUR的水性制备方面使用少量酸(如葡糖酸)的优势，所述疏水性片段具有结构I(其中X＝NR2)。使用布鲁克费尔德粘度计，3号转子和6rmp测量粘度。
表1-具有和不具有葡糖酸的实例4HEUR的水性溶液粘度
| 实例4聚合物(重量％) | 水(重量％) | 葡糖酸(重量％) | 水性溶液粘度(cP) | pH |
| 20％ | 80％ | 0 | 凝胶 | 约7.9 |
| 20％ | 78％ | 2％ | 3309 | 3.62 |
TERGITOL、TAMOL和RHOPLEX均是陶氏化学公司或其附属公司的商标。
实例5-制备聚芳基烷氧基化物和氨基HEUR
在真空中在间歇熔融反应器中，将CARBOWAXTM8000聚乙二醇(PEG；1350g)加热到110℃维持2小时。然后将丁基化羟基甲苯(BHT，0.145g)和Desmodur W(100.53g)添加到反应器中并且搅拌反应混合物5分钟。然后将辛酸铋(28％Bi，3.38g)添加到反应器中，并且在110℃下搅拌所得混合物10分钟。然后将中间物实例3(401.86g)和2-[双(2-乙基己基)氨基]乙醇(19.92g)添加到反应器中并且在110℃下搅拌所得混合物10分钟。将所得熔融聚合物从反应器中移出并冷却。通过如上文所述的SEC测量发现Mw为23,518。通过将聚合物溶解于含有20重量％聚合物固体、20重量％15-S-9和60重量％水的水中来制备水性增稠剂组合物。
实例6.制备氨基聚芳基烷氧基化HEUR
在真空中在间歇熔融反应器中，将CARBOWAXTM8000聚乙二醇(PEG；1200g)加热到110℃维持2小时。然后将丁基化羟基甲苯(BHT，0.132g)和Desmodur W(114.9g)添加到反应器中并且搅拌反应混合物5分钟。然后将辛酸铋(28％Bi，3.0g)添加到反应器中，并且在110℃下搅拌所得混合物10分钟。然后将中间物实例5(554.95g)添加到反应器中并且在110℃下搅拌所得混合物10分钟。将所得熔融聚合物从反应器中移出并冷却。通过将聚合物溶解于具有葡糖酸的水中来制备水性增稠剂组合物。表2为未增稠的着色基底油漆配制物，即无着色剂和HEUR流变改性剂的油漆的配方。
表2-未增稠的着色基底油漆配制物
RHOPLEX和ACRYSOL均是陶氏化学公司或其附属公司的商标。
油漆着色数据
表3a和3b说明深色基底油漆配制物的KU粘度，所述油漆配制物如表2中所描述而制备，并且分别用市售HEUR(ACRYSOLTMRM 995流变改性剂(RM-995)，一种陶氏化学公司或其附属公司的商标或本发明HEUR来增稠，和随后用12盎司Colortrend 808炭黑着色。所有油漆均用ICI增稠剂，ACRYSOLTMRM-3030流变改性剂(RM-3030)共增稠。实验HEUR和RM-3030的量以有效的磅/100加仑(lbs/100gal)为单位。在所有油漆中使用足够的RM-3030以将油漆的稠度调节到ICI粘度在1.1到1.3泊范围内。在室温下使用布鲁克费尔德KU-1+粘度计或等效KU粘度计测量油漆的KU粘度。
表3a-用炭黑着色的HG-706配制物的KU粘度数据
表3b-用炭黑着色的HG-706配制物的KU粘度数据
ΔKU是指通过在从着色前油漆原始KU粘度减去着色KU粘度而得到的用炭黑着色后油漆的KU粘度变化。
实例1-6的油漆配制物中使用的HEUR在添加着色剂后呈现油漆KU粘度稳定性的显著改进。在添加12盎司炭黑着色剂到116盎司油漆基底中后，用RM-995增稠的油漆下降多达27个KU单位。相比而言，用HEUR实例2增稠的油漆在着色时仅下降8个KU单位，用HEUR实例4增稠的油漆在着色时仅下降4个KU单位，且用实例3HEUR增稠的油漆在着色时呈现相当恒定的KU粘度，因为KU实际上稍微增加了1.2个KU单位。
Claims (7)
1.一种化合物，其包含具有由结构I表示的疏水性片段的疏水改性环氧烷聚合物：
其中虚线表示所述片段与所述疏水改性环氧烷聚合物的连接点；Ar1为未被取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；或被1到3个C1-C6烷基或烷氧基取代的苯基、萘基、苯基-O-CH2-、苯基-CH2-O-CH2-或萘基-O-CH2-；并且Ar2为苯基、苯基-OCH2CH2-、苯基-(OCH2CH2)y-、苄基、萘基、萘基-CH2-、萘基-OCH2CH2-或萘基-(OCH2CH2)y-，其中Ar2的苯基或萘基部分未被取代或被1到3个C1-C6烷基取代；其中y为2到10；每一R1独立地是H或C1-C6烷基；X是O或NR2，其中R2是H、C1-C6烷基、苯基或苄基；m是1到20；并且n是0到100。
2.根据权利要求1所述的化合物，其中Ar1为苯基-O-CH2-或邻-甲基苯基-O-CH2-；Ar2为苯基、苄基、苯基-OCH2CH2-或邻-甲基苯基；每一R1独立地为H或CH3；m为1到10；且n为0到40；其中所述疏水改性环氧烷聚合物为疏水改性环氧烷氨基甲酸酯聚合物。
3.根据权利要求2所述的化合物，其中所述疏水性片段的数均分子量(Mn)在500到10,000g/mol范围内；并且X为O或N-CH3、N-苯基或N-苄基；其中所述疏水改性环氧烷聚合物为疏水改性环氧乙烷氨基甲酸酯聚合物。
4.根据权利要求3所述的化合物，其中所述疏水性片段的Mn在500到2500g/mol范围内并且选自由以下组成的群组：
其中R1'为H或CH3；且R2'为CH3或苄基。
5.一种组合物，其包含具有以下的水性分散体：a)按所述组合物的重量计，10重量％到60重量％的聚合物颗粒；和b)按所述组合物的重量计，0.05重量％到2重量％的根据权利要求1所述的化合物。
6.根据权利要求1所述的组合物，其包含小于10PVC的TiO2或BsSO4颗粒。
7.根据权利要求5所述的组合物，其进一步包括一或多种选自由以下组成的群组的材料：粘合剂、分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂和不透明聚合物。
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