CN103159911A - 流变改性剂 - Google Patents
流变改性剂 Download PDFInfo
- Publication number
- CN103159911A CN103159911A CN201210541110XA CN201210541110A CN103159911A CN 103159911 A CN103159911 A CN 103159911A CN 201210541110X A CN201210541110X A CN 201210541110XA CN 201210541110 A CN201210541110 A CN 201210541110A CN 103159911 A CN103159911 A CN 103159911A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- glycol
- branching agent
- polyisocyanates
- melt
- 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
Links
- 239000006254 rheological additive Substances 0.000 title description 9
- 239000006085 branching agent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 67
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 35
- -1 polyoxyethylene Polymers 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 15
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- PBJZAYSKNIIHMZ-UHFFFAOYSA-N ethyl carbamate;oxirane Chemical class C1CO1.CCOC(N)=O PBJZAYSKNIIHMZ-UHFFFAOYSA-N 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 claims description 6
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 229940094933 n-dodecane Drugs 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 claims description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000002562 thickening agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000009472 formulation Methods 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 abstract 2
- 239000004814 polyurethane Substances 0.000 abstract 2
- 229920002635 polyurethane Polymers 0.000 abstract 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 229920001515 polyalkylene glycol Polymers 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000008719 thickening Effects 0.000 description 15
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 6
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 5
- 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 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 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
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YZOUYRAONFXZSI-SBHWVFSVSA-N (1S,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-37,39,40,41,42,43,44,45,46,47,48,49-dodecamethoxy-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38-diol Chemical compound O([C@@H]([C@H]([C@@H]1OC)OC)O[C@H]2[C@@H](O)[C@@H]([C@@H](O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3O)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O3)O[C@@H]2CO)OC)[C@H](CO)[C@H]1O[C@@H]1[C@@H](OC)[C@H](OC)[C@H]3[C@@H](CO)O1 YZOUYRAONFXZSI-SBHWVFSVSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-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
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AQKDMKKMCVJJTC-UHFFFAOYSA-N 2-(2-methylpropoxymethyl)oxirane Chemical compound CC(C)COCC1CO1 AQKDMKKMCVJJTC-UHFFFAOYSA-N 0.000 description 1
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
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- 239000004386 Erythritol Substances 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 230000003115 biocidal effect Effects 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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Abstract
流变改性剂。本发明涉及在催化剂的存在下，通过聚合多异氰酸酯支化剂的无溶剂熔体；Mw为2000至11000道尔顿的水溶性聚亚烷基二醇；以及二异氰酸酯来制备疏水改性的环氧烷聚氨酯的方法；其中，所述无溶剂熔体还包含疏水封端剂，或者在加入催化剂之后将疏水封端剂加入所述熔体。通过本发明的方法制备的疏水改性的环氧烷聚氨酯显示优良的ICI/KU性质，并可用作涂料制剂的增稠剂。
Description
技术背景
本发明涉及疏水改性的氨基甲酸酯聚合物，其可用作水性涂料制剂中的流变改性剂。
流变改性剂用于在水性涂料制剂中控制宽剪切速率范围内的粘度。它们可以是缔合性(它们与分散相缔合)或非缔合性的(它们稠化水相)。缔合性增稠剂可衍生自天然产品，如疏水改性的纤维素醚，或者由合成聚合物，如疏水改性的环氧乙烷氨基甲酸酯(HEUR)聚合物制备。关于HEUR聚合物及其制备的典型描述可参见US2009/0318595A1，其描述了通过使聚乙二醇、疏水性醇、二异氰酸酯和三异氰酸酯在单釜式反应中一起反应来形成线型和支化HEUR聚合物的组合。
U.S.4,155,892(Emmons等)描述了在不同的实施例中制备线性和支化HEUR聚合物。
流变改性剂通常分为低剪切速率粘度增强剂(司氏粘度增强剂(Stormerviscosity builders)，也称为KU粘度增强剂)或高剪切速率粘度增强剂(ICI增强剂)。希望在不伴随KU粘度提高的情况下，提高ICI粘度和ICI粘度增强流变改性剂的效率，这是因为KU粘度的提高限制了制剂人员向制剂中添加增强KU的流变改性剂的能力。
市售可得的HEUR聚合物ACRYSOLTM5000和ACRYSOLTM6000流变改性剂(陶氏化学公司(The Dow Chemical Company)或其附属公司的商标)在丙烯酸类半光泽白漆中的ICI粘度分别为1.75和2.40，KU粘度分别为79.3和109.7。与这些已知的流变改性剂相比，得到具有提高的ICI/KU粘度比的疏水改性的氨基甲酸酯聚合物制剂是有益的。
发明内容
本发明通过提供包括如下步骤的方法解决了现有技术中的需求：使多异氰酸酯支化剂的无溶剂熔体、Mw为2000至11000道尔顿的水溶性聚亚烷基二醇以及二异氰酸酯在足以形成疏水改性环氧烷氨基甲酸酯聚合物的条件下与促进聚合的催化剂接触，前提是：1)在所述无溶剂熔体接触所述催化剂之前，所述熔体还包含疏水封端剂；或者2)在所述熔体与所述催化剂接触之后，将疏水封端剂加入所述熔体；其中，二醇与多异氰酸酯支化剂的摩尔当量比为4至20；且总异氰酸酯基团与二醇羟基基团的摩尔当量比为1.1至1.6。
通过本发明的方法制备的疏水改性的环氧烷氨基甲酸酯聚合物可用作涂料制剂的无溶剂增稠剂。
发明详述
本发明是一种包括以下步骤的方法：使多异氰酸酯支化剂的无溶剂熔体、Mw为2000至11000道尔顿的水溶性聚亚烷基二醇以及二异氰酸酯与促进聚合的催化剂在足以形成疏水改性环氧烷氨基甲酸酯聚合物的条件下接触，前提是：1)在所述无溶剂熔体接触所述催化剂之前，所述熔体还包含疏水封端剂；或者2)在所述熔体与所述催化剂接触之后将疏水封端剂加入所述熔体；其中，二醇与多异氰酸酯支化剂的摩尔当量比为4至20；且总异氰酸酯基团与二醇羟基基团的摩尔当量比为1.1至1.6。
文中所用术语“多异氰酸酯支化剂”是含至少三个异氰酸酯基团的化合物。优选的一类多异氰酸酯支化剂的例子包括异氰脲酸酯三聚体和缩二脲三聚体，其特征示于下式：
其中，R是C4-C30-亚烷基，更具体地是C4-C20-亚烷基。本文所用术语“亚烷基”指的是直链、支链或脂环族的二价饱和或部分饱和的烃基或它们的组合。合适的异氰脲酸酯三聚体的特殊例子(优选的)包括HDI异氰脲酸酯(HDI三聚体)和IPDI异氰脲酸酯(IPDI三聚体)。这些氰脲酸酯化合物的结构如下：
本领域普通技术人员认识到异氰脲酸酯三聚体通常包括赋予化合物更高级异氰酸酯官能度的低水平低聚物(五聚体、七聚体等)。因此，术语“异氰酸酯三聚体”可包含三聚体本身或三聚体和其它低聚体的混合物。实际上，由于存在少量高级低聚物，市售可得的HDI三聚体DesmodurN3600多异氰酸酯三聚体的标示当量重量（183g/mol）高于纯三聚体的当量重量（164g/mol）。
异氰酸酯支化剂也可为二异氰酸酯（优选为脂族二异氰酸酯）与多元醇支化剂的反应产物。文中所用的术语“多元醇支化剂”指的是含至少三个羟基基团的化合物。合适的多元醇支化剂的例子包括：三羟甲基丙烷、季戊四醇、丙三醇、赤藓糖醇、山梨糖醇和甘露醇，以及这些化合物的乙氧基化物。
通过脂族二异氰酸酯和多元醇支化剂反应生成的多异氰酸酯支化剂的例子是通过聚氧乙基甘油醚和二异氰酸酯反应生成的多异氰酸酯支化剂。所述聚氧乙基甘油醚的结构如下所示：
其中，每个R1独立地是C4-C20直链、支链、芳族或脂环族基团，或其组合；并且，x+y+z为0至200。
术语“水溶性聚亚烷基二醇”指的是一种或多种水溶性聚环氧乙烷、水溶性聚环氧乙烷/聚环氧丙烷共聚物、水溶性聚环氧乙烷/聚环氧丁烷共聚物和聚环氧乙烷/聚环氧丙烷/聚环氧丁烷三元聚合物。本文所用的术语“环氧丙烷”指的是具有-(OCH2CH2CH2)-和/或-(OCH(CH3)CH2)-重复基团的聚合物。
优选的水溶性聚环氧烷为聚乙二醇，特别是重均分子量为2000至11000道尔顿范围，优选4000至10000道尔顿范围的聚乙二醇。合适的聚乙二醇的例子是PEG8000，作为CARBOWAXTM8000聚乙二醇(陶氏化学公司或其附属公司的商标)市售可得。
所述二异氰酸酯优选为C4-C20脂族或芳族二异氰酸酯或者其组合。本文所用术语“脂族”指的是饱和或部分不饱和的直链、支链、或脂环族或者它们的组合。合适的二异氰酸酯的例子包括：
1,4-丁二异氰酸酯、1,6-己二异氰酸酯、2,2,4-三甲基-1,6-二异氰酸基己烷、1,10-癸二异氰酸酯、4,4’-亚甲基二(异氰酸基环己烷)、1,4-环己二异氰酸酯、异佛尔酮二异氰酸酯、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、二甲苯二异氰酸酯、4-氯-1,3-亚苯基二异氰酸酯、4,4’-二亚苯基二异氰酸酯、4,4’-亚甲基二苯基异氰酸酯、1,5-亚萘基二异氰酸酯和1,5-四氢亚萘基二异氰酸酯。优选为脂族二异氰酸酯，更优选为1,6-己二异氰酸酯和异佛尔酮二异氰酸酯。
本文所用术语“疏水封端剂”指的是包含六个或更多个具有疏水性部分的碳原子并可以与异氰酸酯基团发生反应的单官能化合物；优选的疏水封端剂是醇或其烷氧基化物；胺或其烷氧基化物；或者叔氨醇或其烷氧基化物；更优选地，所述疏水封端剂由下式表示
R1-X-(CH2CHR3-O)m-H；其中，X=O、NH或NR2；R1和R2独立地是直链、支链、环状、芳族C6至C18或其组合；每个R3独立地是H、直链或支链C1-C6、环状C3-C6或苯基；m为0至50，更优选为0至30。
更优选地，所述疏水封端剂是C6-C18醇或其乙氧基化物；C6-C18胺或其乙氧基化物；或者C6-C18叔氨醇或其乙氧基化物。合适的醇的例子包括正辛醇、正壬醇、正癸醇、正十一烷醇、正十二烷醇、2-乙基己醇、2-丁基-1-辛醇和3,7-二甲基-1-辛醇。合适的胺的例子包括正己胺、正辛胺、正癸胺、正十二烷胺、苄胺、二正己胺、2-乙基己基胺、二环己胺和二苄胺。合适的叔氨醇及其烷氧基化物的例子包括二烷胺和环氧化物(epoxies)或烷基缩水甘油醚的反应产物；合适的二烷基胺的例子包括二甲胺、二乙胺、二丙胺、二异丙胺、二丁胺、二戊胺、二己胺、二-(2-乙基己基)胺、二环己胺和二苄胺；合适的环氧树脂的例子包括环氧乙烷、环氧丙烷、环氧丁烷、1,2-环氧癸烷和1,2-环氧十二烷；合适的烷基缩水甘油醚的例子包括异丙基缩水甘油醚、丁基缩水甘油醚、异丁基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚、叔丁基苯基缩水甘油醚。其它合适的烷氧基化疏水封端剂的例子包括支链醇(如2-丁基-1-辛基醇)或直链醇(如正十二烷醇)与环氧乙烷、环氧丙烷或环氧丁烷的产物。
少量非疏水封端剂可任选地与疏水封端剂一同使用，来调节增稠效果以及其它漆制剂的性质。此类非疏水封端剂的例子包括甲氧基化聚乙二醇，如Polyglykol M2000聚乙二醇单甲基醚(momomethyl ether)。
二醇与多异氰酸酯支化剂的摩尔当量比为4至20，优选6至18，更优选6至15。本文中所述术语“摩尔当量比”指的是反应物中羟基或异氰酸酯基的数量。因此，例如，10摩尔聚乙二醇具有两个羟基/摩尔，而1摩尔的三异氰酸酯具有三个异氰酸酯基/摩尔；则二醇羟基与三异氰酸酯基的摩尔当量比为(10×2)/(1×3)=或6.67。
所述疏水改性的环氧烷氨基甲酸酯聚合物能够通过一段式反应(one-stage reaction)制备，其中将多异氰酸酯支化剂、水溶性聚亚烷基二醇、二异氰酸酯和封端剂掺混在一起，并加热至足够形成熔体的温度，通常为70°C至120°C的温度范围，更优选为85°C至115°C的温度范围，然后加入促进形成氨基甲酸酯连接键的合适催化剂。一段式聚合作用中的优选催化剂为铋催化剂，如2-乙基己酸铋，作为辛酸铋液体MSF28%市售可得。
或者，所述聚合物可在两阶段中制备：在第一阶段中，将含有多异氰酸酯支化剂、水溶性聚亚烷基二醇、二异氰酸酯和催化剂的混合物加热至足以形成熔体和聚合化的温度，优选为70°C至120°C的温度范围，更优选为85°C至115°C的温度范围，以形成未封端聚合物中间体。优选地，在所述水溶性聚亚烷基二醇基本上被消耗后加入封端剂，继续反应至完全以形成最终的聚合物。本文所述术语“水溶性聚亚烷基二醇基本上被消耗”指的是，消耗了至少90％，更优选至少95％，最优选至少99％的水溶性聚亚烷基二醇。两段式聚合反应中合适的催化剂的例子包括：铋催化剂，如辛酸铋；锡催化剂，如二月桂酸二丁基锡；汞催化剂，如新癸酸苯基汞；锌催化剂；铅催化剂；叔胺，如三乙胺、二(2-二甲基氨基乙基)甲胺、1,4-二氮杂双环[2.2.2]辛烷、二甲基环己胺和1,8-二氮杂双环[5.4.0]十一碳-7-烯。
通过本发明方法制备的疏水改性的环氧烷氨基甲酸酯聚合物可用作涂料组合物的无溶剂增稠剂，所述涂料组合物可包含一种或多种以下组分：填料；颜料，例如二氧化钛、云母、碳酸钙、二氧化硅、氧化锌、研磨玻璃、三水合铝、滑石、三氧化锑、飞灰和粘土；聚合物包覆的颜料，例如聚合物包覆或部分包覆的颜料颗粒，例如二氧化钛、氧化锌或锌钡白颗粒；吸附或结合在颜料(如二氧化钛)表面的聚合物或聚合物乳剂；空心颜料，包括具有一个或多个空穴的颜料；分散剂，例如氨醇和聚羧酸盐(酯)；表面活性剂；消泡剂；防腐剂，例如杀生物剂、防霉剂、杀真菌剂、除藻剂和它们的组合；流动剂；流平剂；额外的中和剂，例如氢氧化物、胺、氨和碳酸盐(酯)。
虽然在无溶剂条件下根据本发明方法制备了增稠剂，但是在一些情况下，希望在涂料组合物中加入一些溶剂，以提供例如，增强的涂料冻融性质。
实施例
下面的实施例仅是为了阐述，而不是用来限制本发明的范围。
实施例1：多异氰酸酯支化的HEUR聚合物的制备
在以下过程中，PEG:HDI-三聚体的比例为11.5，且总NCO:二醇的比例为1.28。在间歇式熔融反应器中真空加热CARBOWAXTM8000聚乙二醇（PEG，陶氏化学公司或其附属公司的商标，分子量8200；1521.8克，0.3712摩尔当量的OH）至110°C，保持2小时。冷却至85°C之后，加入丁羟甲苯（BHT,0.159克）和癸醇（19.8克，0.1251摩尔当量的OH），将反应搅拌5分钟。然后，加入Desmodur N3600多异氰酸酯（HDI-三聚体,5.91克,0.0323摩尔当量的NCO）和Desmodur H二异氰酸酯（HDI,37.32克,0.4435摩尔当量的NCO），随后搅拌5分钟。然后，向反应器中加入辛酸铋溶液（28%，3.80克）并将所得混合物搅拌10分钟。从反应器中移出所得的熔融聚合物，并冷却。
实施例2-6：多异氰酸酯支化的HEUR聚合物的制备
基本如实施例1所述进行实施例2-5的过程，不同之处在于，PEG:HDI-三聚体的摩尔当量比和总NCO:二醇的摩尔当量比如表一所列。
表一：PEG:HDI和总NCO:二醇的摩尔当量比
实施例6：原位生成的多异氰酸酯支化的HEUR聚合物的制备
在以下过程中，PEG:三醇的比例为11.50，总NCO:(二醇+三醇)的比例为1.28。向设置有冷凝器、热电偶、机械搅拌器和氮气进口的100mL圆底烧瓶中加入三羟甲基丙烷（TMP,1.71克,0.0383摩尔当量的OH）和HDI（51.48克,0.6118摩尔当量的NCO）。将该反应混合物加热至55°C，搅拌直至TMP熔化。冷却至45°C之后，向混浊的反应混合物中加入一滴二月桂酸二丁基锡。该反应混合物的外观立即变为清澈，允许通过放热将反应混合物加热至55°C，之后搅拌并保持该温度15分钟。然后将反应混合物冷却至室温。
在间歇式熔融反应器中将PEG（1502.0克,0.3663摩尔当量的OH）在真空下加热至110°C，保持2小时。冷却至85°C之后，加入BHT（0.157克）和癸醇（21.46克,0.1356摩尔当量的OH），将反应搅拌5分钟。然后，加入上述制得的TMP/HDI反应产物混合物（44.38克），随后搅拌5分钟。然后向反应器中加入辛酸铋溶液（28%，3.76克）并将所得的混合物搅拌10分钟。从反应器中移出所得的熔融的聚合物并冷却。
实施例7：使用叔氨醇制备多异氰酸酯支化的HEUR聚合物
在以下过程中，PEG:HDI-三聚体的比例为15.5，且总NCO:二醇的比例为1.25。在设置有冷凝器和机械搅拌器的圆底烧瓶中，在氮气下加热二戊胺(372.4克)、丁基缩水甘油醚(346.2克)和水(27克)至回流(105至115℃)。5小时后，将混合物冷却至30°C。在30至150°的温度范围内通过真空蒸馏(14mm Hg)除去水和残留的丁基缩水甘油醚之后，分离所得的氨基醇产物。
在间歇式熔融反应器中将PEG（1708.7克,0.4168摩尔当量的OH）真空加热至110°C，保持2小时。冷却至85°C之后，加入BHT（0.18克）和氨基醇（36.04克,0.1255摩尔当量的OH），将反应搅拌5分钟。然后加入HDI-三聚体（4.92克,0.0269摩尔当量的NCO）和HDI（41.46克,0.4927摩尔当量的NCO），之后搅拌5分钟。然后向反应器中加入辛酸铋溶液（28%，4.27克）并将所得混合物搅拌10分钟。从反应器中移出所得的熔融的聚合物并冷却。
比较例1：三羟甲基丙烷支化的HEUR聚合物的制备
在以下比较例中，PEG:三醇的比例为11.50，总NCO:(二醇+三醇)的比例为1.28。在间歇式熔融反应器中将PEG（1590.6克,0.3880摩尔当量的OH）真空加热至110°C，保持2小时。冷却至85°C之后，加入BHT（0.166克）和癸醇（22.73克,0.1436摩尔当量的OH）以及TMP（1.51克,0.0338摩尔当量的OH），将反应搅拌5分钟。然后加入HDI（45.49克,0.5406摩尔当量的NCO），之后搅拌5分钟。然后向反应器中加入辛酸铋溶液（28%，3.98克）并将所得混合物搅拌10分钟。从反应器中移出所得的熔融的聚合物并冷却。
对于漆中增稠剂评价的描述
通过合并表2中的组分制备乳胶漆组合物，预制漆#1(Pre-paint#1)：
表二：预制漆#1配方
| 克鲁诺(Kronos)4311二氧化钛浆料 | 262.8克 |
| 水 | 180.1克 |
| 乙二醇 | 24.3克 |
| ROPAQUETM Ultra不透明聚合物 | 49.7克 |
| RHOPLEXTM SG-30粘合剂 | 420.9克 |
| Drewplus L-475消泡剂 | 4.0克 |
| 泰沙诺酯醇(Texanol)聚结剂 | 19.2克 |
| 曲通(Triton)X-405表面活性剂 | 2.5克 |
| 总计 | 963.5克 |
ROPAQUE和RHOPLEX为陶氏化学公司或其附属公司的商标。
通过向预制漆#1(963.5g)中加入水性增稠剂分散体和水获得配制漆。为了保持完全配制漆的固体含量恒定，加入的增稠剂和水的总重为49.5克。完全配制漆的密度为1013磅/100加仑(1.2千克/升)。完全配制漆的pH范围是8.5至9.0。
通过以下步骤制备配制漆：向963.5克预制漆#1中缓慢加入水性增稠剂分散体(40.0g)和水(9.5g)。将混合物搅拌10分钟。通过向50mL塑料离心管中加入干燥的固体增稠剂蜡(10.0克)、甲基-β-环糊精(1.0克50%的溶液)和水(39.0克)制备水性增稠剂分散体。将所述试管盖上盖子，安装在旋转器上连续翻转超过48小时，直至水性增稠剂分散体变得均匀。在室温下平衡24小时后，在实验室混合器上搅拌增稠的漆1分钟，然后测量粘度值。表3显示了用实施例中的HEUR增稠剂配制的漆的KU、ICI、和ICI/KU值。如表3所示，本发明的方法提供了可用于制备涂料制剂的无溶剂增稠剂，所述涂料制剂具有优良平衡的ICI和KU性质。
表3：半光泽白漆的涂料数据。
通过合并表4中的组分制备乳胶漆组合物，预制漆#2：
表4：预制漆#2配方
TAMOL和RHOPLEX为陶氏化学公司或其附属公司的商标。
通过向预制漆#2(905.4g)中加入实施例7水性增稠剂的分散体和水获得VSR-2015配制漆。为了保持完全配制漆的固体含量恒定，加入的增稠剂和水的总重为158.9克。完全配制漆的密度为1064磅/100加仑(1.3千克/升)。完全配制漆的pH范围为8.5至9.0。
所述配制漆的制备如下：向905.4g预制漆#2中缓慢加入实施例7水性增稠剂的分散体（25.0克）、氨（1.0克）和水（132.9克）。搅拌该混合物10分钟。通过向50mL塑料离心管中加入干燥的固体增稠剂蜡(10.0克)、乳酸(0.5克，85%的固体)和水(39.5克)制备实施例8水性增稠剂的分散体。将所述试管盖上盖子，安装在旋转器上连续翻转超过48小时，直至水性增稠剂分散体变得均匀。在室温下平衡24小时后，在实验室混合器上搅拌增稠的漆1分钟，然后测量粘度值。用实施例7增稠的VSR-2015漆的KU值为110.4，ICI值为2.00，ICI/KU(*100)为1.81。
结果显示，采用本发明方法制备的增稠剂具有优良的ICI和ICI/KU(*100)值。所述方法的另一优点在于无溶剂，这使得不存在或基本不存在挥发性有机溶剂（VOCs）。虽然不希望受理论限制，据认为由于聚合物主链上更多任机分布支化点的存在使得支化点之间的分子量更高和端基疏水物之间的分子量更高，使得本发明的方法提供了改善的ICI/KU平衡。
Claims (9)
1.一种包括如下步骤的方法：使多异氰酸酯支化剂的无溶剂熔体、Mw为2000至11000道尔顿的水溶性聚亚烷基二醇和二异氰酸酯在足以形成疏水改性环氧烷氨基甲酸酯聚合物的条件下与促进聚合的催化剂接触；前提是：1)在所述无溶剂熔体接触所述催化剂前，所述熔体还包含疏水封端剂；或者2)使所述熔体与所述催化剂接触之后，将疏水封端剂加入所述熔体中；
其中，二醇与多异氰酸酯支化剂的摩尔当量比为4至20；并且总异氰酸酯基与二醇羟基基团的摩尔当量比为1.1至1.6。
2.如权利要求1所述的方法，其特征在于，在所述无溶剂熔体与所述催化剂接触前，所述熔体还包含疏水封端剂；所述方法在70°C至120°C的温度范围内进行；所述水溶性聚亚烷基二醇是Mw为4000至10000道尔顿的聚乙二醇；所述催化剂是铋催化剂；其中，所述疏水封端剂是C6-C18-醇或者C6-C18叔氨醇。
3.如权利要求2所述的方法，其特征在于，所述方法在85°C至115°C的温度范围内进行；所述多异氰酸酯支化剂为1,6-己二异氰酸酯的异氰脲酸酯；异佛尔酮二异氰酸酯的异氰脲酸酯；三(异氰酸己酯基)缩二脲；1,6,11-十一烷三异氰酸酯，或者二异氰酸酯和多元醇支化剂的反应产物；所述疏水封端剂至少包含以下一种：正辛醇、正壬醇、正癸醇、正十一烷醇、正十二烷醇、2-乙基己醇、2-丁基-1-辛醇或者3,7-二甲基-1-辛醇；所述催化剂为辛酸铋；
其中，所述二醇中的羟基与多异氰酸酯支化剂中的异氰酸酯基的摩尔当量比为8至16；并且，总异氰酸酯基与二醇羟基的摩尔当量比为1.2至1.4。
4.如权利要求3所述的方法，其特征在于，所述多异氰酸酯支化剂为己二异氰酸酯的异氰脲酸酯、异佛尔酮二异氰酸酯的异氰脲酸酯、或者二异氰酸酯和聚氧乙基甘油醚的反应产物，所述反应产物如下式所示：
其中，每个R1独立是二价的C4-C20直链、支链、或脂环族基团或其组合；并且，x+y+z的范围是0至200。
5.如权利要求1所述的方法，其特征在于，所述疏水封端剂是在所述熔体接触所述催化剂之后加入所述熔体中的C6-C18醇；所述方法在70°C至120°C的温度范围内进行；所述水溶性聚亚烷基二醇是Mw为4000至10000道尔顿的聚乙二醇；所述催化剂为叔胺或锡、铋或锌催化剂。
6.如权利要求5所述的方法，其特征在于，所述方法在85°C至115°C的温度范围内进行；所述多异氰酸酯支化剂为己二异氰酸酯的异氰脲酸酯；异佛尔酮二异氰酸酯的异氰脲酸酯；三(异氰酸己酯基)缩二脲；1,6,11-十一烷三异氰酸酯，或者二异氰酸酯和多元醇支化剂的反应产物；所述C6-C18醇至少包括以下一种：正辛醇、正壬醇、正癸醇、正十一烷醇、正十二烷醇、2-乙基己醇、2-丁基-1-辛醇或3,7-二甲基-1-辛醇；所述催化剂为辛酸铋；
其中，二醇与多异氰酸酯支化剂的摩尔当量比为8至16；并且，总异氰酸酯基团与二醇羟基的摩尔当量比为1.2至1.4。
7.如权利要求5或6所述的方法，其特征在于，所述多异氰酸酯支化剂为己二异氰酸酯的异氰脲酸酯、异佛尔酮二异氰酸酯的异氰脲酸酯、或者二异氰酸酯和聚氧乙基甘油醚的反应产物，其反应产物如下式所示：
其中，每个R1独立是二价的C4-C20直链、支链、或脂环族基团或其组合；并且，x+y+z的范围是0至200。
8.如权利要求2所述的方法，其特征在于，所述C6-C18叔氨醇为二戊胺和丁基缩水甘油醚的反应产物；所述催化剂为辛酸铋。
9.一种组合物，所述组合物包含粘合剂、颜料和用权利要求1～7中任一项所述方法制备的疏水改性的环氧烷氨基甲酸酯聚合物。
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| CA3178671A1 (en) * | 2020-05-26 | 2021-12-02 | Marisa HOSTETTER | Rheology modifier and aminosilane waterborne admixture |
| FR3111893B1 (fr) * | 2020-06-30 | 2023-04-28 | Coatex Sas | Composé triuréthane modificateur de rhéologie |
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| AU2023367479A1 (en) | 2022-10-26 | 2025-04-24 | Ppg Industries Ohio, Inc. | Coating composition for use in high efficiency applicators |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349451A (zh) * | 2015-07-14 | 2017-01-25 | 罗门哈斯公司 | 用于制备疏水改性环氧烷氨基甲酸酯聚合物的方法 |
| CN106349451B (zh) * | 2015-07-14 | 2020-11-13 | 罗门哈斯公司 | 用于制备疏水改性环氧烷氨基甲酸酯聚合物的方法 |
| CN106916274A (zh) * | 2015-12-28 | 2017-07-04 | 陶氏环球技术有限责任公司 | 用于抗粘连性及凝固时间的聚醚‑氨基甲酸酯‑脲添加剂 |
| CN106916274B (zh) * | 2015-12-28 | 2021-04-20 | 陶氏环球技术有限责任公司 | 用于抗粘连性及凝固时间的聚醚-氨基甲酸酯-脲添加剂 |
| CN109749628A (zh) * | 2017-11-03 | 2019-05-14 | 陶氏环球技术有限责任公司 | 具有用疏水性低聚物改性的聚(氧化烯-氨基甲酸乙酯)缔合型增稠剂的着色基础涂料制剂 |
| CN109749628B (zh) * | 2017-11-03 | 2022-12-23 | 陶氏环球技术有限责任公司 | 具有用疏水性低聚物改性的聚(氧化烯-氨基甲酸乙酯)缔合型增稠剂的着色基础涂料制剂 |
| CN115087710A (zh) * | 2020-03-31 | 2022-09-20 | 科莱恩国际有限公司 | 疏水改性聚氨酯增稠剂及其制备方法 |
| CN115087710B (zh) * | 2020-03-31 | 2024-03-01 | 科莱恩国际有限公司 | 疏水改性聚氨酯增稠剂及其制备方法 |
| CN112225877A (zh) * | 2020-09-04 | 2021-01-15 | 华南理工大学 | 一种三官能度异氰酸酯改性聚氨酯增稠剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX338528B (es) | 2016-04-20 |
| KR101504488B1 (ko) | 2015-03-20 |
| JP2013127056A (ja) | 2013-06-27 |
| KR20130069449A (ko) | 2013-06-26 |
| CA2795088C (en) | 2015-12-29 |
| CN103159911B (zh) | 2016-03-02 |
| CA2795088A1 (en) | 2013-06-14 |
| EP2604637A1 (en) | 2013-06-19 |
| US20130158194A1 (en) | 2013-06-20 |
| JP5542897B2 (ja) | 2014-07-09 |
| AU2012258362A1 (en) | 2013-07-04 |
| AU2012258362B2 (en) | 2014-06-26 |
| EP2604637B1 (en) | 2017-05-17 |
| BR102012031525B1 (pt) | 2020-03-03 |
| BR102012031525A2 (pt) | 2013-10-01 |
| MX2012013914A (es) | 2013-06-17 |
| US9150683B2 (en) | 2015-10-06 |
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