CN117567721A - 一种多嵌段的聚酯树脂及其制备方法和应用 - Google Patents
一种多嵌段的聚酯树脂及其制备方法和应用 Download PDFInfo
- Publication number
- CN117567721A CN117567721A CN202311420520.3A CN202311420520A CN117567721A CN 117567721 A CN117567721 A CN 117567721A CN 202311420520 A CN202311420520 A CN 202311420520A CN 117567721 A CN117567721 A CN 117567721A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- parts
- chain extender
- crown
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 63
- 239000004645 polyester resin Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 239000004970 Chain extender Substances 0.000 claims abstract description 40
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 33
- -1 amine compounds Chemical class 0.000 claims abstract description 31
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 2
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229960002479 isosorbide Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 27
- 229920000728 polyester Polymers 0.000 abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 239000004576 sand Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000002253 acid Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 230000003111 delayed effect Effects 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- QIMNMSOZIDDLGN-UHFFFAOYSA-N N#CO.N#CO.C(C1CCCCC1)C1CCCCC1 Chemical compound N#CO.N#CO.C(C1CCCCC1)C1CCCCC1 QIMNMSOZIDDLGN-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920000162 poly(ureaurethane) Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明属于涂料技术领域,特别涉及一种多嵌段的聚酯树脂及其制备方法和应用。一种多嵌段的聚酯树脂,其原料组分包括胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂。本发明通过胺类化合物、异氰酸酯缩聚、扩链剂、异氰酸酯缩聚、封端剂形成聚脲‑聚氨酯‑聚酯结构,三嵌段结构的微相分离效应可以终止涂层形变过程中银纹生长,使聚酯具有良好的抗冲击、抗折弯性能、延时抗折弯性能、延时冲击性能及较低的涂层光泽度。同时,利用冠醚和胺类化合物分子中的N‑H键或O‑H键的自组装作用形成有序的冠醚/胺类包合物,利用聚合后的冠醚/高分子套锁结构,提高涂层的抗冲击、抗折弯性能及韧性。
Description
技术领域
本发明属于涂料技术领域,特别涉及一种多嵌段的聚酯树脂及其制备方法和应用。
背景技术
砂纹粉末涂料可以产生美观清晰的图案,赋予产品多彩的外观,通过纹理效果既可以掩盖基材表面缺陷,又可提高涂膜的装饰性能和抗划伤性能,达到普通粉末涂料无法达到的装饰效果和功能性,因此在家电、防盗门、卷材、灯饰等领域具有广泛的应用。
砂纹粉末涂料一般是在粉末涂料中加入砂纹剂及砂纹助剂,粉末涂料在熔融流动过程中,由于砂纹剂的表面张力低于粉末涂料基料的正常表面张力,分散在涂层各点的砂纹剂改变了涂层的局部张力,使表面张力高的基料包裹表面张力低的砂纹剂,最终使涂层膜呈现均匀分布的砂粒形状。然而密集的应力集中点容易使涂层在折弯、冲压过程中形成裂痕,造成涂层的开裂脱落,使砂纹粉末涂料在后加工领域的应用受限。
目前,有采用多种树脂构建互穿交联结构的研究,使得涂层在高膜厚的条件下具有良好的延展性和高附着力,另外,搭配木质素磺酸钠、聚乙二醇和硅藻土等添加剂进一步提高涂层强度,使砂纹涂层在高膜厚(100微米以上)条件下仍具有极佳的抗冲击性能,但涂层的延时机械性能不能满足要求。虽然有研究所制得的粉末涂料在存放3个月后仍具有良好的机械性能,但其所用的聚酯的酸值较高(43-47mgKOH/g),需消耗较多固化剂,且固化剂TGIC具有一定毒性,对人体和环境有害。同时,通过引入核壳结构增韧剂可获得聚酯/环氧体系的砂纹粉末涂料,并可提高涂料和基材的附着力,但固化后涂层仅能通过+50kg·cm冲击,抗冲击性较差。
因此,亟需提供一种聚酯树脂,其应用于涂料中后所得到的涂层具有优异的冲击性能、抗折弯性能、延时冲击性能、延时抗折弯性能,能够满足后加工成型的应用要求,且砂纹质感强,光泽度低,柔韧性好。
发明内容
本发明旨在解决现有技术中存在的一个或多个技术问题,至少提供一种有益的选择或创造条件。本发明提供一种多嵌段的聚酯树脂,其应用于涂料中后所得到的涂层砂纹质感强,光泽度低,柔韧性好,且具有优异的冲击性能、抗折弯性能、延时冲击性能、延时抗折弯性能,能够满足后加工成型的应用要求。
本发明的发明构思:本发明通过胺类化合物和异氰酸酯缩聚,引入脲基;扩链剂和异氰酸酯缩聚,引入聚氨酯;封端剂的酯化反应,引入聚酯。脲基极大地提高了聚酯的极性,在低砂纹剂用量下也能实现优异的砂纹效果,并减少涂层中的应力集中点,提高涂层的韧性;另外,聚脲和聚氨酯结构,使得涂料对基材的附着力更好,且具有更优异的耐低温性能。即本发明通过树脂多层次结构设计形成了聚脲-聚氨酯-聚酯的软硬结构,三嵌段结构的微相分离效应可以终止涂层形变过程中银纹生长,使聚酯具有良好的抗冲击、抗折弯性能、延时冲击性能、延时抗折弯性能及较低的涂层光泽。同时,本发明利用冠醚和胺类化合物分子中的N-H键或O-H键的自组装作用形成有序的冠醚/胺类包合物,聚合后的冠醚/高分子套锁结构一方面可有效阻止冲击、折弯过程中分子链的滑移和断裂,提高冲击性能和抗折弯性能,另一方面,冠醚的两亲特性增加了高极性多嵌段聚酯树脂和砂纹剂之间的界面相容性,进而提高涂层韧性。
因此,本发明的第一方面提供一种多嵌段的聚酯树脂。
具体的,一种多嵌段的聚酯树脂,其原料组分包括胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂;
所述第一扩链剂为非聚合物多元醇;所述第二扩链剂为聚合物多元醇。
优选地,所述多嵌段的聚酯树脂的酸值为23-40mgKOH/g。
进一步优选地,所述多嵌段的聚酯树脂的酸值为25-40mgKOH/g。
优选地,所述多嵌段的聚酯树脂的熔融粘度为3500-22000mPa·s;玻璃化转变温度为50-80℃;数均分子量为1800-17000。
进一步优选地,所述多嵌段的聚酯树脂的熔融粘度为4000-20000mPa·s;玻璃化转变温度为55-75℃;数均分子量为2000-16000。
优选地,按重量份计,所述多嵌段的聚酯树脂的原料组分包括胺类化合物1.8-22份、冠醚0.09-7.0份、异氰酸酯9-65份、第一扩链剂0.9-18份、第二扩链剂0.9-11份、封端剂9-45份。
进一步优选地,按重量份计,所述多嵌段的聚酯树脂的原料组分包括胺类化合物2-20份、冠醚0.1-5.5份、异氰酸酯10-60份、第一扩链剂1-15份、第二扩链剂1-10份、封端剂10-40份。
优选地,所述多嵌段的聚酯树脂的原料组分还包括催化剂、固化促进剂中的至少一种。
优选地,所述多嵌段的聚酯树脂的原料组分还包括催化剂和固化促进剂;且按重量份计,所述多嵌段的聚酯树脂的原料组分包括胺类化合物1.8-22份、冠醚0.09-7.0份、异氰酸酯9-65份、第一扩链剂0.9-18份、第二扩链剂0.9-11份、封端剂9-45份、催化剂0.0002-0.002份、固化促进剂0.0001-0.0016份。
进一步优选地,按重量份计,所述多嵌段的聚酯树脂的原料组分包括胺类化合物2-20份、冠醚0.1-5.5份、异氰酸酯10-60份、第一扩链剂1-15份、第二扩链剂1-10份、封端剂10-40份、催化剂0.0002-0.001份、固化促进剂0.0001-0.0015份。
优选地,所述胺类化合物选自乙醇胺、二乙醇胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、间苯二甲胺、哌嗪、二氨基二苯醚中的至少一种。
优选地,所述冠醚选自15-冠-5、苯并15-冠-5、18-冠-6、二环已烷并-18-冠-6、二苯并18-冠-6中的至少一种。
优选地,所述异氰酸酯选自二苯基甲烷二异氰酸酯、二环己基甲烷二氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、对苯二异氰酸酯中的至少一种。
优选地,所述第一扩链剂选自乙二醇、丙二醇、二甘醇、甲基丙二醇、新戊二醇、丁二醇、1,2-丙二醇、1,4-环己烷二甲醇、异山梨醇、2-甲基-2,4-戊二醇、乙基丁基丙二醇、三羟甲基丙烷、季戊四醇中的至少一种;和/或,所述第二扩链剂选自聚酯型多元醇、聚醚型多元醇、聚丙二醇、聚丁二醇、聚己内酯多元醇中的至少一种。
优选地,所述第二扩链剂的数均分子量为450-2200,羟值为9-450mgKOH/g。
进一步优选地,所述第二扩链剂的数均分子量为500-2000,羟值为10-400mgKOH/g。
优选地,所述封端剂选自间苯二甲酸、丁二酸、己二酸、十二烷二酸、偏苯三酸酐、均苯四甲酸二酐中的至少一种。
优选地,所述催化剂包括酯化催化剂。
优选地,所述酯化催化剂包括锡催化剂、锌催化剂、铋催化剂、钛催化剂中的至少一种。
优选地,所述锡催化剂包括单丁基氧化锡、单丁基氯化锡、草酸亚锡、辛酸亚锡、氯化亚锡、二丁基锡二月桂酸酯、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的至少一种。
优选地,所述锌催化剂包括异辛酸锌、草酸锌中的至少一种。
优选地,所述铋催化剂包括氧化铋。
优选地,所述钛催化剂包括二氧化钛。
优选地,所述固化促进剂包括三苯基乙基溴化膦、三苯基膦中的至少一种。
本发明的第二方面提供一种本发明第一方面所述的多嵌段的聚酯树脂的制备方法。
具体的,所述多嵌段的聚酯树脂的制备方法,包括以下步骤:
将各原料组分混合,反应,制得所述多嵌段的聚酯树脂。
优选地,所述多嵌段的聚酯树脂的制备方法,包括以下步骤:
(1)将所述胺类化合物、冠醚混合,反应,得到包合物;
(2)将剩余组分加入到步骤(1)所得的所述包合物中,制得所述多嵌段的聚酯树脂。
优选地,步骤(1)中,将胺类化合物、有机溶剂、冠醚混合,反应,得到包合物。
优选地,步骤(1)中,先将装有胺类化合物的容器抽真空,然后关闭真空,充入惰性气体,再加入有机溶剂、冠醚混合,反应,得到包合物。
优选地,所述有机溶剂选自甲苯、二甲苯、四氢呋喃、乙酸乙酯、乙酸丁酯、正丁醇、1,4-二氧六环、异丙醇、丙酮、丁酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的至少一种。
优选地,所述有机溶剂的用量与所述胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂的总质量比为(0.9-17)mL:0.9-1.1g。
进一步优选地,所述有机溶剂的用量与所述胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂的总质量比为(1-15)mL:lg。
优选地,步骤(1)中,所述反应的温度为4-85℃,所述反应的时间为0.4-1.7h;进一步优选地,所述反应的温度为5-80℃,所述反应的时间为0.5-1.5h。
优选地,步骤(2)的制备过程具体为:
S1:将所述催化剂、异氰酸酯加入步骤(1)所得的所述包合物中,反应,得到第一混合物;
S2:将所述第一扩链剂和第二扩链剂加入步骤S1所得的所述第一混合物中,反应,得到第二混合物;
S3:将所述封端剂加入步骤S2所得的所述第二混合物中,反应,然后加入固化促进剂,制得所述多嵌段的聚酯树脂。
优选地,步骤S1中,所述反应的温度为4-130℃,所述反应的时间为1.8-6.5h;进一步优选地,所述反应的温度为5-120℃,所述反应的时间为2-6h。
优选地,步骤S2中,所述反应的温度为4-200℃,所述反应的时间为0.4-3.5h;进一步优选地,所述反应的温度为5-180℃,所述反应的时间为0.5-3h。
优选地,步骤S3中,所述反应的温度为55-250℃,所述反应的时间为0.4-3.5h;进一步优选地,所述反应的温度为60-230℃,所述反应的时间为0.5-3h。
优选地,步骤S3中,所述反应结束后,体系的酸值为18-65mgKOH/g;进一步优选地,所述反应结束后,体系的酸值为20-60mgKOH/g。
优选地,步骤S3中,所述反应结束后,还包括抽真空的过程。
优选地,所述抽真空后,体系的酸值为25-40mgKOH/g。
优选地,所述抽真空的时间为0.4-5.5h;进一步优选地,所述抽真空的时间为0.5-5h。
优选地,步骤S3中,抽真空结束后,加入固化促进剂,制得所述多嵌段的聚酯树脂。
本发明的第三方面提供一种涂料。
具体的,所述涂料包括本发明第一方面所述的多嵌段的聚酯树脂。
优选地,所述涂料还包括固化剂、颜填料和助剂。
优选地,按重量份计,所述涂料包括多嵌段的聚酯树脂50-75份、固化剂1.5-10份、颜填料13-47份和助剂0.1-5.5份。
进一步优选地,按重量份计,所述涂料包括多嵌段的聚酯树脂55-70份、固化剂2-8份、颜填料15-43份和助剂0.2-5份。
优选地,所述固化剂选自异氰尿酸三缩水甘油酯、羟烷基酰胺中的至少一种。
优选地,所述颜填料选自炭黑、铁黄、铁红、酞菁绿、钛白粉、硫酸钡、云母粉、碳酸钙、二氧化硅、滑石粉中的至少一种。
优选地,所述助剂选自砂纹剂、流平剂、光亮剂、安息香、膨润土中的至少一种。
优选地,所述砂纹剂选自偏氟聚合物、含氟改性聚合物中的至少一种;进一步优选地,所述砂纹剂为捷通达SA2072。
优选地,所述流平剂为聚丙烯酸酯类流平剂;进一步优选地,所述流平剂为南海化学GLP588。
优选地,所述光亮剂为丙烯酸丁酯和甲基丙烯酸甲酯的共聚物;进一步优选地,所述光亮剂为南海化学701B。
优选地,所述膨润土为蒙脱石有机铵衍生物。
本发明的第四方面提供一种涂料在防盗门、电梯门、防火门、铝天花、家用电器领域中的应用。
相对于现有技术,本发明提供的技术方案的有益效果如下:
(1)本发明通过胺类化合物、异氰酸酯缩聚、扩链剂、异氰酸酯缩聚、封端剂相互作用形成一种聚脲-聚氨酯-聚酯的软硬结构,三嵌段结构的微相分离效应可以终止涂层形变过程中银纹生长,使聚酯具有良好的抗冲击性能、抗折弯性能、延时抗冲击性能、延时抗折弯性能及较低的涂层光泽度。同时,本发明利用冠醚和胺类化合物分子中的N-H键或O-H键的自组装作用形成有序的冠醚/胺类包合物,聚合后的冠醚/高分子套锁结构一方面可有效阻止冲击、折弯过程中分子链的滑移和断裂,提高冲击性能和抗折弯性能,另一方面,冠醚的两亲特性增加了多嵌段聚酯和砂纹剂之间的界面相容性,提高涂层韧性。
(2)本发明制备工艺相较于常规聚酯熔融缩聚法(反应温度在235℃以上),反应温度较低,且加入有机溶剂后更有利于反应物的分散,保证聚合产物兼具较高的分子量和较窄的分子量分布,从而提高粉末涂层的韧性。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案,现列举以下实施例进行说明。需要指出的是,以下实施例对本发明要求的保护范围不构成限制作用。
以下实施例中所用的原料、试剂或装置如无特殊说明,均可从常规商业途径得到,或者可以通过现有已知方法得到。
本发明实施例1-4多嵌段的聚酯树脂的各原料组分及用量如表1所示。
表1:实施例1-4多嵌段的聚酯树脂的各原料组分及用量
实施例1
一种多嵌段的聚酯树脂,按重量份计,其原料组分包括表1中的各原料组分和用量。
一种多嵌段的聚酯树脂的制备方法,包括以下步骤:
(1)将装有胺类化合物的容器抽真空,然后关闭真空,充入惰性气体,加入冠醚、各原料组分(胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂)总质量10倍体积的有机溶剂N-甲基吡咯烷酮,搅拌混合,在25℃温度下反应1h,得到包合物;
(2)将催化剂、异氰酸酯依次加入步骤(1)所得的包合物中,在25℃的温度下反应5h,得到第一混合物;
(3)将第一扩链剂和第二扩链剂加入步骤(2)所得的第一混合物中,在80℃的温度下反应2.5h,得到第二混合物;
(4)将封端剂加入步骤(3)所得的第二混合物中,在200℃的温度下反应2h,控制酸值在50mgKOH/g;然后抽真空(真空度为-0.096MPa)3h,排除有机溶剂和缩聚形成的副产物、低聚物和水蒸汽等小分子,酸值达到32mgKOH/g,最后加入固化促进剂,得到多嵌段的聚酯树脂。
实施例2
一种多嵌段的聚酯树脂,按重量份计,其原料组分包括表1中的各原料组分和用量。
实施例2多嵌段的聚酯树脂的制备方法的步骤(4)中,在200℃的温度下反应2h,控制酸值在51mgKOH/g;然后抽真空(真空度为-0.096MPa)3h,排除有机溶剂和缩聚形成的副产物、低聚物和水蒸汽等小分子,酸值达到33mgKOH/g,其他同实施例1。
实施例3
一种多嵌段的聚酯树脂,按重量份计,其原料组分包括表1中的各原料组分和用量。
实施例3多嵌段的聚酯树脂的制备方法的步骤(4)中,在200℃的温度下反应2h,控制酸值在48mgKOH/g;然后抽真空(真空度为-0.096MPa)3h,排除有机溶剂和缩聚形成的副产物、低聚物和水蒸汽等小分子,酸值达到32mgKOH/g,其他同实施例1。
实施例4
一种多嵌段的聚酯树脂,按重量份计,其原料组分包括表1中的各原料组分和用量。
实施例4多嵌段的聚酯树脂的制备方法的步骤(4)中,在200℃的温度下反应2h,控制酸值在50mgKOH/g;然后抽真空(真空度为-0.096MPa)3h,排除有机溶剂和缩聚形成的副产物、低聚物和水蒸汽等小分子,酸值达到32mgKOH/g,其他同实施例1。
对比例1
对比例1和实施例1的区别仅在于,对比例1没有添加冠醚,其他同实施例1。
对比例2
对比例2和实施例2的区别仅在于,对比例2采用等量的乙二醇替换乙二胺,其他同实施例2。
对比例3
对比例3和实施例3的区别仅在于,对比例3采用等量的二环己烷二甲酸替换二环己基甲烷二氰酸酯,其他同实施例3。
对比例4
对比例4为市售的砂纹粉末涂料专用聚酯神剑SJ4E,酸值为33.2mgKOH/g,粘度为7300mPa·s。
性能测试
1.聚酯树脂的酸值、粘度、玻璃化转变温度测试
按照T/GDTL 004-2019标准,对实施例1-4所制备的多嵌段的聚酯树脂进行酸值、粘度、玻璃化转变温度的测试,结果如表2所示。
表2:实施例1-4的多嵌段的聚酯树脂的酸值、粘度、玻璃化转变温度
测试项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
酸值(mgKOH/g) | 34.1 | 33.3 | 34.5 | 32.3 |
粘度(mPa.s)/200℃ | 6600 | 9200 | 5900 | 8500 |
玻璃化温度(Tg)(℃) | 63 | 69 | 60 | 65 |
2.涂料性能测试
取实施例1-4、对比例1-3的聚酯树脂、对比例4的市售产品各285份,分别与15份羟烷基酰胺(HAA)、100份钛白粉、97份硫酸钡、1份砂纹剂SA2072、2份流平剂南海化学GLP588混合均匀,分别采用螺杆挤出机进行熔融、挤出、压片、破碎,并将片料粉碎过筛制成粉末,得到涂料粉末;其中,螺杆挤出机的工艺参数控制为:1区温度100℃;2区温度105℃;螺杆转速40HZ。然后采用静电喷枪分别将制备的涂料粉末喷涂在经表面除油除锈的马口铁上,涂装参数为:静电电压70kV,输粉气压0.05MPa,得到的涂层厚度为65μm,在180℃的温度下烘烤固化10min后,进行性能测试,测试结果如表3所示。
其中,测试项目及测试方法如下:
表面外观:采取目测;
光泽度:按照GB/T 9754-2007标准进行测试,采用60°入射角测试;
冲击性能:按照T/GDTL004-2009标准进行测定;
抗折弯性能:按照NCAAⅡ-19标准进行测定;
延时冲击性能和延时抗折弯性能:在常温、常温下放置90天后进行冲击性能和抗折弯性能测试。
表3:实施例1-4、对比例1-3的聚酯树脂、对比例4的市售产品所制备的涂料的性能
由表3测试结果可以看出,本发明采用多嵌段的聚酯树脂所得到的涂层具有良好的冲击性能、抗折弯性能、砂纹质感和消光性能,且涂层在3个月后仍具有优异的抗折弯性能和冲击性能,即具有良好的延时抗折弯性能和延时冲击性能。
对比例1由于没有添加冠醚,使得对比例1涂层的延时抗折弯性能和延时冲击性能均差于实施例1。对比例2由于采用等量的乙二醇替换乙二胺,使得对比例2涂层的冲击性能、抗折弯性能、延时抗折弯性能和延时冲击性能及光泽度均差于实施例2。说明胺类化合物和冠醚具有协同效应,其共同作用使得涂层具有良好的冲击性能、抗折弯性能、延时抗折弯性能和延时冲击性能,并且可降低涂层光泽度,具有良好的消光效果,缺少任何一种均会使涂层的性能变差。
对比例3采用等量的二环己烷二甲酸替换二环己基甲烷二氰酸酯,使得对比例3的砂纹质感、光泽度、延时冲击性能、抗折弯性能、延时抗折弯性能均差于实施例3。因为缺少异氰酸酯时,胺类化合物和异氰酸酯、扩链剂和异氰酸酯无法完成缩聚,无法在聚酯树脂的结构中引入了脲基、聚氨酯,进而无法得到聚脲-聚氨酯-聚酯的软硬结构,使得涂层的性能变差。
对比例4采用市面常规的聚酯树脂,由于其不具备聚脲和聚氨酯结构,其所得到的涂层的机械性能、延时机械性能、砂纹质感、光泽度均明显差于本发明多嵌段的聚酯树脂所制备的涂层的性能。
以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种聚酯树脂,其特征在于,其原料组分包括胺类化合物、冠醚、异氰酸酯、第一扩链剂、第二扩链剂、封端剂;
所述第一扩链剂为非聚合物多元醇;所述第二扩链剂为聚合物多元醇。
2.根据权利要求1所述的聚酯树脂,其特征在于,按重量份计,所述聚酯树脂的原料组分包括胺类化合物1.8-22份、冠醚0.09-7.0份、异氰酸酯9-65份、第一扩链剂0.9-18份、第二扩链剂0.9-11份、封端剂9-45份。
3.根据权利要求1-2任一项所述的聚酯树脂,其特征在于,所述聚酯树脂的原料组分还包括催化剂、固化促进剂中的至少一种。
4.根据权利要求3所述的聚酯树脂,其特征在于,所述胺类化合物选自乙醇胺、二乙醇胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、间苯二甲胺、哌嗪、二氨基二苯醚中的至少一种。
5.根据权利要求3所述的聚酯树脂,其特征在于,所述冠醚选自15-冠-5、苯并15-冠-5、18-冠-6、二环已烷并-18-冠-6、二苯并18-冠-6中的至少一种。
6.根据权利要求3所述的聚酯树脂,其特征在于,所述异氰酸酯选自二苯基甲烷二异氰酸酯、二环己基甲烷二氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、对苯二异氰酸酯中的至少一种。
7.根据权利要求3所述的聚酯树脂,其特征在于,所述第一扩链剂选自乙二醇、丙二醇、二甘醇、甲基丙二醇、新戊二醇、丁二醇、1,2-丙二醇、1,4-环己烷二甲醇、异山梨醇、2-甲基-2,4-戊二醇、乙基丁基丙二醇、三羟甲基丙烷、季戊四醇中的至少一种;和/或,所述第二扩链剂选自聚酯型多元醇、聚醚型多元醇、聚丙二醇、聚丁二醇、聚己内酯多元醇中的至少一种。
8.权利要求1-7任一项所述的聚酯树脂的制备方法,其特征在于,包括以下步骤:
将各原料组分混合,反应,制得所述聚酯树脂。
9.根据权利要求8所述的制备方法,其特征在于,包括以下步骤:
(1)将所述胺类化合物、冠醚混合,反应,得到包合物;
(2)将剩余组分加入到步骤(1)所得的包合物中,制得所述聚酯树脂。
10.一种涂料,其特征在于,包括权利要求1-7任一项所述的聚酯树脂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311420520.3A CN117567721A (zh) | 2023-10-30 | 2023-10-30 | 一种多嵌段的聚酯树脂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311420520.3A CN117567721A (zh) | 2023-10-30 | 2023-10-30 | 一种多嵌段的聚酯树脂及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117567721A true CN117567721A (zh) | 2024-02-20 |
Family
ID=89863394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311420520.3A Pending CN117567721A (zh) | 2023-10-30 | 2023-10-30 | 一种多嵌段的聚酯树脂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117567721A (zh) |
-
2023
- 2023-10-30 CN CN202311420520.3A patent/CN117567721A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1754737B1 (en) | Polyester resin and thermosetting aqueous coating composition | |
EP1788049B1 (en) | Thermosetting aqueous coating composition | |
JP6752800B2 (ja) | ウレタン樹脂粒子 | |
WO2012002569A1 (en) | Method for forming multilayer coating film | |
EP3733797B1 (en) | Coating material composition | |
EP3486292B1 (en) | Coating composition | |
JP5614537B2 (ja) | 耐チッピング性塗料組成物 | |
JP2006111853A (ja) | 塗料組成物 | |
WO2019181990A1 (ja) | 複層塗膜形成方法 | |
JP5626795B2 (ja) | 複層塗膜形成方法 | |
CN117567721A (zh) | 一种多嵌段的聚酯树脂及其制备方法和应用 | |
WO2009075392A1 (en) | Coating composition and method for forming multilayer coating film | |
CN114736604B (zh) | 一种高固体分dtm聚氨酯涂料及其制备方法 | |
JP2017101233A (ja) | 中塗り塗料組成物 | |
CN113930101B (zh) | 一种pp基材和abs基材通用的附着力促进剂及其制备方法 | |
CA3130043C (en) | Rheology control agent and paint composition | |
JP2012087183A (ja) | 耐傷性に優れるコーティング樹脂組成物 | |
CN115572523B (zh) | 一种聚酯树脂组合物、涂料和应用 | |
JP7408586B2 (ja) | 塗料組成物 | |
CN114853742B (zh) | 一种改性hdi脲二酮固化剂的制备方法与应用 | |
EP3660063A1 (en) | Curable coating composition | |
CN118185437A (zh) | 一种聚脲超耐磨地坪涂料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |