CN106255711A - 用于聚合物多元醇制备方法的稳定剂 - Google Patents
用于聚合物多元醇制备方法的稳定剂 Download PDFInfo
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- CN106255711A CN106255711A CN201580023607.4A CN201580023607A CN106255711A CN 106255711 A CN106255711 A CN 106255711A CN 201580023607 A CN201580023607 A CN 201580023607A CN 106255711 A CN106255711 A CN 106255711A
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- Prior art keywords
- stabilizer
- weight
- macromonomer
- polyhydric alcohol
- initiator
- Prior art date
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 96
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 50
- 229920005862 polyol Polymers 0.000 claims description 42
- 150000005846 sugar alcohols Polymers 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 150000003077 polyols Chemical class 0.000 claims description 30
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 11
- -1 azo isobutyronitrile Chemical compound 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N alpha-isobutyric acid Natural products CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- 238000012546 transfer Methods 0.000 claims 2
- 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 claims 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 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000000600 sorbitol Substances 0.000 claims 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000010526 radical polymerization reaction Methods 0.000 description 11
- 238000004945 emulsification Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- RTNSFNKPBIASPV-UHFFFAOYSA-N (1-isocyanato-2-methylprop-2-enyl)benzene Chemical class O=C=NC(C(=C)C)C1=CC=CC=C1 RTNSFNKPBIASPV-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical class CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHRUXMWFDWRUNK-UHFFFAOYSA-N 4-isocyanato-2-methylidenebutanoic acid Chemical compound OC(=O)C(=C)CCN=C=O BHRUXMWFDWRUNK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 241000292525 Titanio Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- RDMCIZBQFMGFOF-UHFFFAOYSA-N [Eu].FC(C(=O)O)(F)F Chemical compound [Eu].FC(C(=O)O)(F)F RDMCIZBQFMGFOF-UHFFFAOYSA-N 0.000 description 1
- KHAXJHNCVIBENA-UHFFFAOYSA-N [Ho].CS(=O)(=O)O.[F] Chemical compound [Ho].CS(=O)(=O)O.[F] KHAXJHNCVIBENA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920005628 alkoxylated polyol Polymers 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000707 boryl group Chemical group B* 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- CDYCKNMKRGFHPW-UHFFFAOYSA-N dysprosium;trifluoromethanesulfonic acid Chemical compound [Dy].OS(=O)(=O)C(F)(F)F CDYCKNMKRGFHPW-UHFFFAOYSA-N 0.000 description 1
- FECRNHPJGAZUKO-UHFFFAOYSA-N erbium;trifluoromethanesulfonic acid Chemical compound [Er].OS(=O)(=O)C(F)(F)F FECRNHPJGAZUKO-UHFFFAOYSA-N 0.000 description 1
- SPWBJDZFBWHQGT-UHFFFAOYSA-N europium;trifluoromethanesulfonic acid Chemical compound [Eu].OS(=O)(=O)C(F)(F)F SPWBJDZFBWHQGT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- NAPHXISIYHAKAH-UHFFFAOYSA-N lanthanum;trifluoromethanesulfonic acid Chemical compound [La].OS(=O)(=O)C(F)(F)F NAPHXISIYHAKAH-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- QYHYRWWBPOPMLX-UHFFFAOYSA-N neodymium;trifluoromethanesulfonic acid Chemical compound [Nd].OS(=O)(=O)C(F)(F)F QYHYRWWBPOPMLX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VPPWQRIBARKZNY-UHFFFAOYSA-N oxo(diphenyl)tin Chemical compound C=1C=CC=CC=1[Sn](=O)C1=CC=CC=C1 VPPWQRIBARKZNY-UHFFFAOYSA-N 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical compound [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- DXZODPQHLDOQFU-UHFFFAOYSA-N praseodymium;trifluoromethanesulfonic acid Chemical compound [Pr].OS(=O)(=O)C(F)(F)F DXZODPQHLDOQFU-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AXXFVUWEFGKYBC-UHFFFAOYSA-N samarium;trifluoromethanesulfonic acid Chemical compound [Sm].OS(=O)(=O)C(F)(F)F AXXFVUWEFGKYBC-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- OGEJCBGPTKTKHE-UHFFFAOYSA-N terbium;trifluoromethanesulfonic acid Chemical compound [Tb].OS(=O)(=O)C(F)(F)F OGEJCBGPTKTKHE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- C08G18/28—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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/636—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the presence of a dispersion-stabiliser
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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Abstract
本发明涉及一种用于聚合物多元醇制备方法的稳定剂、其制备和用途。
Description
本发明涉及一种用于聚合物多元醇制备方法的稳定剂、其制备和用途。
特别地,本发明的稳定剂适于稳定通过熔融乳化(melt emulsification)制备的聚合物多元醇分散体。
在本上下文中,术语“熔融乳化”指的是仅包括组分的物理混合,而不包括化学反应的一种方法。
在WO2009/155427中,术语熔融乳化定义如下:
分散预先形成的聚合物的另一方式是将其熔化,然后在剪切下将熔化的聚合物与多元醇共混。剪切作用将熔化的聚合物破碎成分散在多元醇相中的小液滴。该方法记载于美国专利第6,623,827号中。该份专利记载了这样一种方法,其中在挤出机中将预先形成的聚合物熔化,与表面活性剂和聚醚多元醇混合,随后与更多的聚醚多元醇混合。然后使混合物冷却以固化颗粒。
术语稳定剂可定义为通过以下获得的化合物:使具有反应性不饱和度的大分子单体(macromere)与苯乙烯和丙烯腈在聚醚多元醇中反应,任选地可使用链转移剂。本发明的稳定剂用于通过熔融乳化法制备含D50小于25μm、优选小于10μm、最优选小于5μm的小颗粒的聚合物多元醇,且其应当能够将聚合物多元醇分散体稳定较长时间(防止相分离)。
稳定作用通过将样品储存较长时间并在通常六个月的储存期之前和之后对其进行视觉观察而确定。如果在样品容器的底部没有形成沉淀(即无相分离),那么认为样品稳定,并由此认为稳定剂起作用。
本质上,本发明的稳定剂不同于EO1675885、US6013731、5990185或EP0786480中记载的通过自由基聚合而预先形成的用于标准接枝工艺的稳定剂。对通过自由基聚合形成并稳定聚合物多元醇分散体的方法的要求和挑战是根本不同的。
EP 1 506 240 A0公开了通过连续法制备的接枝多元醇。该方法为利用自由基聚合获得最终聚合物多元醇产物的标准方法。于是,由于所述方法不是熔融乳化法,因此EP 1506 240 A0的稳定剂不同于用于熔融乳化法的稳定剂。由于使用少量的大分子单体(16%,基于TMI和聚醚多元醇计),导致较差的性能(非有效的相稳定)。
WO2012154393记载了通过使不饱和聚醚与低分子量单体以可控自由基聚合共聚而制备的聚合物稳定剂。该聚合物稳定剂用于通过机械分散方法或原位聚合方法制备聚合物多元醇产物。与通过可控自由基聚合获得的稳定剂相比,通过自由基聚合获得的稳定剂在其结构上具有较大的可变性。通过自由基聚合和可控自由基聚合制备的稳定剂是根本不同的。分子量分布、副产物、分子量等非常不同。即便是通过这两种方法获得的具有相似组成的产物,它们也不能相比。
相比于WO2012154393,本发明除其他外记载了通过大分子单体的自由基聚合而得的稳定剂的合成,所述大分子单体用于自由基聚合。将该产物用于熔融乳化法中,以获得含苯乙烯-丙烯腈共聚物作为分散相的聚合物多元醇产物。
本发明的一个方面为合成稳定剂,所述稳定剂将苯乙烯-丙烯腈共聚物的分散体有效稳定在聚醚相中。可示出,利用通过该方法获得的这些稳定剂而得到的分散体具有小的粒度,并且具有改善的长期稳定性。
可示出,对于稳定作用而言,本发明的稳定剂的组成是重要的。出人意料地,单体苯乙烯与丙烯腈之间的比例并非必须与使用的SAN材料的比例相匹配才能获得稳定的分散体。
因此,本发明的目的是一种稳定剂(S),优选用于熔融乳化法来制备聚合物多元醇,其包含基于所有组分之和计10重量%至70重量%、优选30重量%至60重量%、更优选40重量%至55重量%的至少一种多元醇P2,以及至少一种多元醇CSP,所述多元醇CSP包含至少一种大分子单体M、苯乙烯和丙烯腈在P2中任选地与引发剂和/或链转移剂的反应产物,其中所述稳定剂(S)的大分子单体M的含量基于所有组分之和计为30重量%至70重量%、优选35重量%至54重量%,和/或其中所述多元醇CSP优选为梳形结构。
在本公开内容中,术语“稳定剂”(S)一般意义上指的是化学化合物。
稳定剂(S)是被认为稳定聚醚相中的苯乙烯-丙烯腈共聚物分散体,并由此被认为稳定聚合物多元醇分散体的化合物。特别地,认为稳定剂(S)稳定通过熔融乳化法获得的聚合物多元醇分散体。
本发明的其他目的还有在至少一种多元醇P2的存在下通过苯乙烯、丙烯腈和至少一种大分子单体M的自由基聚合而制备本发明的稳定剂(S)的方法,以及通过熔融乳化而制备聚合物多元醇分散体的方法,其中使用本发明的稳定剂(S)。
所述多元醇P2通常选自聚醚多元醇(PEOL),优选选自分子量Mn为1000g/mol至6000g/mol的PEOL,更优选选自分子量为2000g/mol至5000g/mol的PEOL。Mn可通过如下所述测定。
WO 2002/28937记载了在用于PU应用的稳定分散体中使用的稳定剂。这些稳定剂被记载为优选基本不含官能团。与该公开相比,本文中所述的本发明的稳定剂含有OH官能团,通过与所使用的载体多元醇相互作用,所述OH官能团可提高所获得分散体的储存稳定性。另外,所述稳定剂的OH官能团会在PU反应期间与异氰酸酯相互作用,并会使得SAN颗粒在PU基质中的嵌入获得改善。
如上所述,在优选实施方案中,本发明的稳定剂中包含的多元醇CSP为梳形结构。
在该优选的梳形结构中,两个大分子单体之间的常规距离为16个苯乙烯和丙烯腈单元至最高达500个苯乙烯和丙烯腈单元,优选30个苯乙烯和丙烯腈单元至最高达200个苯乙烯和丙烯腈单元。
图1示出了梳形结构多元醇CSP(21)的示例性实施方案,所述梳形结构多元醇CSP(21)为本发明的稳定剂(S)的优选实施方案的组分,其中(22)指的是由苯乙烯和丙烯腈构成的共聚物链,(23)表示大分子单体单元。
EP 1 675 885给出了术语预先形成的稳定剂的定义:
预先形成的稳定剂(PFS)特别可用于制备在高固含量下具有较低粘度的聚合物多元醇。在预先形成的稳定剂的方法中,使大分子单体与单体反应以形成由大分子单体和单体构成的共聚物。这些包含大分子单体和单体的共聚物通常被称为预先形成的稳定剂(PFS)。可以控制反应条件,使得一部分共聚物由溶液中沉淀而形成固体。在许多应用中,得到具有低固含量(例如3重量%至15重量%)的分散体。优选地,控制反应条件而使得粒度小,从而使颗粒能够在聚合物多元醇反应中起到“晶种”的作用。
例如,美国专利5,196,476公开了在自由基聚合引发剂和液体稀释剂的存在下,通过使大分子单体与一种或多种烯属不饱和单体聚合而制备的预先形成的稳定剂组合物,在所述液体稀释剂中所述预先形成的稳定剂基本不溶解。EP 0,786,480公开了一种通过以下制备预先形成的稳定剂的方法,在自由基引发剂的存在下,在包含至少30重量%(基于多元醇的总重量计)的偶合多元醇的液体多元醇的存在下,使得5重量%至40重量%的一种或多种烯属不饱和单体聚合,所述偶合多元醇可以具有诱导不饱和度。这些预先形成的稳定剂可用于制备稳定且具有窄的粒度分布的聚合物多元醇。所述偶合多元醇对于实现该预先形成的稳定剂的小粒度(优选0.1微米至0.7微米)是必需的。美国专利6,013,731和5,990,185还公开了包含多元醇、大分子单体、至少一种烯属不饱和单体和自由基聚合引发剂的反应产物的预先形成的稳定剂组合物。
已知体积庞大的分子为有效的大分子单体,因为可使用更少的物质来空间性地稳定颗粒。例如,参见EP 0786480。一般而言,这是因为高支化聚合物具有比直链分子(例如一元醇)明显更大的排除体积,因而需要的支链聚合物较少。美国专利5,196,476公开了2及更高、优选3及更高的官能度适于制备大分子单体。
基于多官能多元醇且具有多个反应性不饱和位点的大分子单体记载于美国专利5,196,476中。如该文献中所记载,当通过马来酸酐路径制备大分子单体时,存在不饱和浓度的上限。如果每摩尔多元醇的不饱和摩尔比例过高,则更可能会形成每分子具有多于一个双键的物种。通常,‘476专利采用对于每摩尔的烷氧基化多元醇加合物,约0.5摩尔至约1.5摩尔、优选约0.7摩尔至约1.1摩尔的反应性不饱和化合物。
如上所述,本领域原则上已知预先形成的稳定剂(PFS),用于通过自由基聚合形成分散体的方法。然而,对熔融乳化法中所要使用的稳定剂的要求是不同的(即使稳定剂的制备可能类似)。
熔融乳化法仅包括组分的物理混合,而不包括化学反应。在常规方法(自由基聚合)中,在自由基聚合期间将PFS或大分子单体加入。因此,停留的时间不同,并且在熔融乳化法中不存在后聚合或另外的聚合物链生长。
另外,认为本发明的稳定剂优选含有类梳形结构的多元醇CSP。认为这些多元醇CSP具有由苯乙烯/丙烯腈(SAN)聚合物形成的主链,所述苯乙烯/丙烯腈(SAN)聚合物与待稳定的聚合物多元醇产物中所含的SAN相互作用。此外,用于合成本发明的稳定剂的大分子单体通常具有这样的官能团,其被认为与待稳定的聚合物多元醇产物的多元醇相互作用,并在PU反应期间可与异氰酸酯反应。该方法改善了接枝颗粒在PU网络中的结合。
在25℃下,本发明的稳定剂通常具有的粘度为1000mPas至100000mPas,优选5000mPas至80000mPas,更优选8000mPas至60000mPas。
本发明的稳定剂的OH数通常为1mg KOH/g至100mg KOH/g,优选1mg KOH/g至50mgKOH/g,更优选10mg KOH/g至40mg KOH/g。
羟基数根据2012年的DIN 53240(DIN=“Deutsche Industrienorm”,即德国工业标准)测定。
除非另外指出,多元醇的粘度在25℃下根据1994年的DIN EN ISO3219,通过Rheotec RC20旋转粘度计使用CC 25DIN转子(转子直径:12.5mm;量筒内径:13.56mm),全部在100/1s(而非50/1s)的剪切速率下测定。
在本发明的稳定剂的优选实施方案中,苯乙烯与丙烯腈的比例大于1:1,优选大于1:1.5,最优选大于1:2。
本文中所述的本发明稳定剂(S)的合成通常是在自由基引发剂和任选地链转移剂的存在下,通过使大分子单体或大分子单体混合物与苯乙烯和丙烯腈在载体多元醇(P2)中进行自由基聚合反应而完成。该反应通常以半间歇法进行;但也可以为间歇法或连续法。可在反应之前、期间或之后将单体、大分子单体或大分子单体混合物、载体多元醇、引发剂或链转移剂连续地或逐步地加入到反应器中。
可使用不同的自由基引发剂,例如偶氮衍生物如AIBN,过氧化物如叔戊基过氧化物、氢过氧化物和过碳酸盐。最优选的是偶氮衍生物,特别是AIBN(偶氮异丁腈)和/或二甲基2,2'-偶氮双(2-甲基丙酸酯)。
本发明的稳定剂可用于稳定聚合物多元醇分散体,特别是通过熔融乳化制备的聚合物多元醇分散体。
在优选实施方案中,当使用本发明的稳定剂时,所得的聚合物多元醇分散体的固含量为10%至50%,优选30%至46%,在25℃和100 1/s剪切速率下的粘度为1000mPas至20000mPas,优选3000mPas至15000mPas,更优选5000mPas至12000mPas。
为测定固含量,将聚合物多元醇样品加入到离心管中,在离心管中用溶剂将其稀释并充分摇匀;将混合物用高速离心机离心分离,并通过倾倒而将上层清液移出离心管;将上述整个过程重复至少两次,然后将盛有样品的离心管置于真空炉中干燥;冷却至室温后,对离心管中剩余的固体进行称重,以计算样品中的固含量。
本发明的稳定剂的粒度D50优选小于0.5μm,更优选小于0.3μm(将样品用异丙醇稀释以得到适于测量的光学浓度后,使用Mastersizer 2000(Malvern Instruments Ltd)通过静态激光衍射测定。对于样品的分散,使用2500rpm搅拌速率的分散模组Hydro SM。粒度分布的计算可以通过Mastersizer 2000利用Fraunhofer理论进行)。
大分子单体的合成:
大分子单体定义为包含一个或多个能够与乙烯基单体如苯乙烯和丙烯腈共聚的可聚合双键,并且包含一个或多个羟基封端的聚醚链的分子。常规的大分子单体包括具有不饱和基团的聚醚多元醇,所述具有不饱和基团的聚醚多元醇通常通过使标准聚醚多元醇与有机化合物反应来制备,所述有机化合物含有不饱和基团及羧基、酸酐、异氰酸酯、环氧或其他能够与活性含氢基团反应的官能团。可用的异氰酸酯包括异氰酸根合乙基丙烯酸甲酯(IEM)和1,1-二甲基间异丙烯基苄基异氰酸酯(TMI)。
在本发明的优选实施方案中,将TMI用于制备大分子单体。通常,大分子单体在Lewis酸催化剂的存在下合成。
合适的Lewis酸催化剂通常包括锡基、硼基、铝基、镓基、稀土基、锌基或钛基化合物。代表性的锡基化合物包括:二乙酸二丁基锡、二溴化二丁基锡、二氯化二丁基锡、二月桂酸二丁基锡、二甲氧基二丁基锡、氧化二丁基锡、二乙酸二甲基锡、二溴化二甲基锡、二氯化二苯基锡、二苯基氧化锡、三氯化甲基锡、三氯化苯基锡、乙酸锡(IV)、溴化锡(IV)、氯化锡(IV)、碘化锡(IV)、氧化锡(II)、乙酸锡(II)、溴化锡(II)、氯化锡(II)、碘化锡(II)和2-乙基己酸锡(II)(辛酸亚锡)。表性的硼基化合物包括:三溴化硼、三氯化硼、三氟化硼和三(五氟苯基)硼烷。代表性的铝基化合物包括:氯化铝和溴化铝。代表性的镓基化合物包括:氯化镓、溴化镓和乙酰丙酮镓(III)。
代表性的稀土催化剂通常为钪、钇、镧、镨、钕、铒、铥、镱、钕或镥的盐。实例包括:三氟甲磺酸镱、乙酰丙酮镱(III)、三氟磺酸铒(III)(三氟甲磺酸铒)、乙酰丙酮铒(III)、三氟甲磺酸钬、三氟甲磺酸铽、三氟甲磺酸铕、三氟乙酸铕(III)、三氟甲磺酸钐、三氟甲磺酸钕、乙酰丙酮钕(III)、三氟甲磺酸镨、三氟甲磺酸镧和三氟甲磺酸镝。代表性的锌基化合物包括氯化锌和溴化锌。代表性的钛化合物包括溴化钛(lV)和氯化钛(lV)。
本领域中已知多种用于将反应性不饱和度引入多元醇中的方法。有用的大分子单体的合成记载于WO2005/003200中。大分子单体A为通过三官能聚醚多元醇与1,1-二甲基间异丙烯基苄基异氰酸酯(TMI)的反应而获得的产物。大分子单体B为通过六官能聚醚多元醇与1,1-二甲基间异丙烯基苄基异氰酸酯(TMI)的反应而获得的产物。
多元醇的分子量通常可通过下式计算:Mn=f×56100/OH值,其中Mn=数均分子量,以g/mol计;f=官能度,每分子的OH基团数目,由用于合成大分子单体的起始物决定;OH值=低聚多元醇的羟基数,以mg KOH/g计。
使用至少一种本发明的稳定剂进行稳定的聚合物多元醇分散体可用于制备聚氨酯(PU)。
通常,在聚氨酯的制备中,任选地在至少一种发泡剂和/或催化剂的存在下,使至少一种多元醇与至少一种聚异氰酸酯或异氰酸酯反应。
在该PU制备方法中,常规的A组分由一种或多种多元醇、一种或多种聚氨酯催化剂、一种或多种表面活性剂、一种或多种交联剂、水或任选地其他化学或物理发泡剂组成。B组分通常含有异氰酸酯。
在本发明的另一个实施方案中,在PU制备方法中,也可以使用包含本发明的稳定剂的聚合物多元醇来获得稳定的A组分,使得A组分可以储存更长时间而不发生相分离。
实施例:
在以下部分,给出一些实验实施例以说明本发明的一些方面。
合成稳定剂的一般方法:
使玻璃反应器盛装载体多元醇、任选地(初始即为)大分子单体或大分子单体混合物、任选地丙烯腈、任选地苯乙烯、任选地链转移剂,并将该玻璃反应器加热至125℃。将载体多元醇、引发剂、苯乙烯、丙烯腈以及大分子单体或大分子单体混合物的混合物经100分钟加入。将反应混合物在125℃下再搅拌20分钟。随后在125℃下将该混合物减压抽真空120分钟以去除残留的单体。表征所获得的稳定剂,并且不经进一步纯化而使用。
通过该方法获得的代表性稳定剂的组成示于表x中。所有的量均以重量%计。所有实验均使用0.5重量%的偶氮引发剂(二甲基2,2'-偶氮双(2-甲基丙酸酯)和0.4%的含硫醇链转移剂进行。该部分中给出的重量百分比是指最终产物(即稳定剂)的。
表1
剩余部分(当总计为100重量%时其余的)由引发剂(单数种或复数种)和链转移剂(单数种或复数种)组成。
多元醇分散体的制备:
以下分散体通过使用市售的具有不同苯乙烯和丙烯腈组成的苯乙烯-丙烯腈共聚物类型而获得。例如可使用购自Samsung的类型、购自Styrolution的类型、购自Ineos的类型。使配备搅拌器和氮气入口的圆底烧瓶盛装200g表x中给出的SAN类型和50g所选择的稳定剂,并在氮气气氛下加热至245℃。将混合物在该温度下搅拌15分钟。将2095加热至245℃,并在剧烈搅拌下加入。加入后将混合物额外搅拌30分钟,然后冷却至RT。如前所述,粒度通过光散射测定。将粒度用作稳定剂体系的效率的指标。
与实施例4相比,实施例1至3表明,对于所制备分散体的有效稳定而言,用于合成稳定剂的苯乙烯、丙烯腈、大分子单体或大分子单体混合物以及载体多元醇之间的比例是重要的。实施例4中使用的稳定剂3表明,使用大量的苯乙烯和丙烯腈制备稳定剂会导致用这些产物得到的分散体的稳定性效率低。使用稳定剂4的实施例5和使用稳定剂7的实施例8表明,对于获得有效的稳定剂体系而言,所使用大分子单体的量至关重要。
用于制备稳定剂的单体苯乙烯与丙烯腈之间的比例,其并非必须与所使用的SAN材料的比例相匹配才能获得稳定的分散体。实施例2和7中所用稳定剂的苯乙烯与丙烯腈比例为1.86比1,用作分散相的SAN的组成为3.16比1。在这两种情况下,均可获得具有小粒度的非常稳定的分散体。稳定剂6不能用于制备分散体,因为该稳定剂的粘度高。在常规条件下无法处理这些高粘性的稳定剂。
Claims (21)
1.稳定剂(S),其包含基于所有组分之和计10重量%至70重量%、优选30重量%至60重量%、更优选40重量%至55重量%的至少一种多元醇P2,以及至少一种多元醇CSP,所述多元醇CSP包含至少一种大分子单体M、苯乙烯和丙烯腈在P2中任选地与引发剂和/或链转移剂的反应产物,其中所述稳定剂(S)的大分子单体M的含量基于所有组分之和计为35重量%至54重量%,和/或其中所述多元醇CSP优选为梳形结构,其中所述稳定剂(S)的苯乙烯的全部含量为4重量至15重量%,和/或所述稳定剂(S)的丙烯腈的全部含量为2重量至7重量%,并且其中所述大分子单体M通过,任选地在Lewis酸催化剂的存在下,使1,1-二甲基间异丙烯基苄基异氰酸酯(TMI)与聚醚多元醇PM反应而获得。
2.权利要求1的稳定剂(S),其由一种或两种多元醇P2和一种或两种多元醇CSP组成,所述多元醇CSP包含至少一种大分子单体M、苯乙烯和丙烯腈在P2中任选地与引发剂和/或链转移剂的反应产物,所述引发剂选自偶氮引发剂和过氧化物引发剂,所述链转移剂选自十二烷基硫醇、异丙醇和2-丁醇。
3.权利要求1或2的稳定剂(S),其由一种或两种多元醇P2、一种或两种多元醇CSP组成,所述多元醇CSP由大分子单体M、苯乙烯和丙烯腈在P2中的反应产物组成。
4.权利要求1至3中任一项的稳定剂(S),其中所述大分子单体M的平均分子量Mn为1000g/mol至50000g/mol,优选2000g/mol至30000g/mol,更优选3000g/mol至20,000g/mol。
5.权利要求1至4中任一项的稳定剂(S),其中所述大分子单体M具有每分子平均0.2至1.2个可聚合烯属不饱和基团,和/或每分子2至8个羟基。
6.权利要求1至5中任一项的稳定剂(S),其中在所述大分子单体M的制备中使用的聚醚多元醇PM选自三官能聚醚多元醇和六官能聚醚多元醇,优选选自丙三醇、山梨糖醇和1,1,1-三羟甲基丙烷(TMP)。
7.权利要求1至6中任一项的稳定剂(S),其中苯乙烯与丙烯腈的比例大于1:1,优选大于1:1.5,最优选大于1:2。
8.权利要求1至7中任一项的稳定剂(S),其中所述稳定剂在25℃下根据DIN EN ISO3219和100 1/s剪切速率测定的粘度为1000mPas至100000mPas,优选5000mPas至80000mPas。
9.权利要求1至8中任一项的稳定剂(S),其中所述稳定剂(S)的多元醇P2的总含量为20重量%至70重量%,优选32重量%至55重量%。
10.权利要求1至9中任一项的稳定剂(S),其中不使用额外的溶剂。
11.在至少一种多元醇P2的存在下,通过苯乙烯、丙烯腈和至少一种大分子单体M的自由基聚合而制备权利要求1至10中任一项的稳定剂(S)的方法,其中所述大分子单体M通过,任选地在Lewis酸催化剂的存在下,使1,1-二甲基间异丙烯基苄基异氰酸酯(TMI)与聚醚多元醇PM反应而获得。
12.权利要求11的制备稳定剂(S)的方法,其中使用至少一种链转移剂,所述链转移剂优选选自硫醇和具有小于200g/mol的MW的低分子量醇。
13.权利要求11或12的制备稳定剂(S)的方法,其中至少一种、优选全部链转移剂选自十二烷基硫醇、异丙醇和2-丁醇。
14.权利要求11至13中任一项的制备稳定剂(S)的方法,其中总共使用小于5重量%,优选小于2重量%的所述链转移剂,相对于全部的反应混合物的重量计。
15.权利要求11至14中任一项的制备稳定剂(S)的方法,其中反应温度为80℃至150℃,优选90℃至130℃,和/或反应进行10分钟至300分钟,优选50分钟至200分钟。
16.权利要求11至15中任一项的制备稳定剂(S)的方法,其中使用至少一种引发剂,所述引发剂优选选自偶氮引发剂或过氧化物,特别优选偶氮异丁腈(AIBN)和/或二甲基2,2'-偶氮双(2-甲基丙酸酯)。
17.权利要求11至16中任一项的制备稳定剂(S)的方法,其中总共使用小于1重量%的所述引发剂,相对于全部的反应混合物的重量计。
18.权利要求1至10中任一项的和/或通过权利要求12至18中任一项的方法获得的稳定剂(S)用于稳定通过熔融乳化制备的聚合物多元醇分散体的用途。
19.通过熔融乳化制备聚合物多元醇分散体的方法,其中使用权利要求1至10中任一项的和/或通过权利要求12至18中任一项的方法获得的稳定剂(S)。
20.权利要求19的通过熔融乳化制备聚合物多元醇分散体的方法,其中获得的聚合物多元醇分散体的固含量为10%至50%,优选30%至46%,和/或在25℃下的粘度为1000mPas至20000mPas,优选3000mPas至15000mPas,更优选5000mPas至12000mPas,和/或平均粒度为D50<50μm。
21.通过权利要求19至20中任一项的方法可获得的聚合物多元醇用于制备聚氨酯的用途。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN1653100A (zh) * | 2002-05-15 | 2005-08-10 | 巴斯福公司 | 通过连续方法制备的接枝多元醇 |
US20130281627A1 (en) * | 2012-04-18 | 2013-10-24 | Bayer Materialscience Llc | Preformed stabilizers useful for the production of polymer polyols and polymer polyols produced therefrom |
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US5196476A (en) | 1990-06-12 | 1993-03-23 | Arco Chemical Technology, L.P. | Polymer/polyol and preformed stabilizer systems |
ES2148397T3 (es) | 1995-10-10 | 2000-10-16 | Bayer Ag | Procedimiento continuo para la preparacion de polioles polimericos de baja viscosidad, finamente divididos, muy estables, de pequeño tamaño medio de particulas. |
DE69514693T2 (de) | 1995-10-23 | 2000-09-07 | Dow Chemical Co | Polymer-polyol sowie vorgeformte stabilisierungssysteme |
JPH09309937A (ja) | 1996-01-29 | 1997-12-02 | Shell Internatl Res Maatschappij Bv | ポリマーポリオール及びポリマーポリオールの製造方法 |
EP1130045B2 (en) * | 2000-02-29 | 2015-10-28 | Nippon Shokubai Co., Ltd. | Process for producing a water-absorbent resin powder |
CN1249164C (zh) | 2000-10-05 | 2006-04-05 | 陶氏环球技术公司 | 预聚物在多元醇中的分散体 |
US6475588B1 (en) | 2001-08-07 | 2002-11-05 | General Electric Company | Colored digital versatile disks |
US7148288B2 (en) | 2003-06-27 | 2006-12-12 | Basf Corporation | Process for formation of preformed stabilizer polyols |
CN100491442C (zh) * | 2003-08-21 | 2009-05-27 | 中国石化集团天津石油化工公司 | 聚合物多元醇的制备方法 |
US20050085613A1 (en) | 2003-10-16 | 2005-04-21 | Adkins Rick L. | Novel unsaturated macromers for preformed stabilizers and polymer polyols |
US20060083694A1 (en) * | 2004-08-07 | 2006-04-20 | Cabot Corporation | Multi-component particles comprising inorganic nanoparticles distributed in an organic matrix and processes for making and using same |
US20070060690A1 (en) * | 2005-09-09 | 2007-03-15 | Bayer Materialscience Llc | Low viscosity polymer polyols characterized by a high hydroxyl number |
EP2041198A1 (en) * | 2006-07-05 | 2009-04-01 | Dow Global Technologies Inc. | Copolymer polyols and a process for the production thereof |
JP2009244551A (ja) * | 2008-03-31 | 2009-10-22 | Konica Minolta Business Technologies Inc | 画像表示装置用表示粒子および画像表示装置 |
ATE552283T1 (de) | 2008-06-19 | 2012-04-15 | Dow Global Technologies Llc | Schmelzdispersionsverfahren zur herstellung von polymerpolyolen |
EP2707409B1 (en) | 2011-05-12 | 2015-03-04 | Dow Global Technologies LLC | Stabilizer polymerization process and process for making polymer polyols |
RU2713651C2 (ru) * | 2014-04-30 | 2020-02-06 | Басф Се | Способ получения полимерного полиола |
RU2017122384A (ru) * | 2014-11-27 | 2018-12-27 | Басф Се | Получение полимерных полиолов в ненасыщенных полиолах, полимерные полиолы и их применение |
-
2015
- 2015-04-28 US US15/307,242 patent/US10472458B2/en active Active
- 2015-04-28 WO PCT/EP2015/059148 patent/WO2015165878A1/en active Application Filing
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- 2015-04-28 CN CN201580023607.4A patent/CN106255711A/zh active Pending
- 2015-04-28 CN CN201910424893.5A patent/CN110156949B/zh active Active
- 2015-04-28 KR KR1020167032894A patent/KR102475640B1/ko active IP Right Grant
- 2015-04-28 RU RU2016146798A patent/RU2692255C2/ru active
- 2015-04-28 MX MX2016014227A patent/MX2016014227A/es unknown
- 2015-04-28 EP EP15717925.0A patent/EP3137527B1/en active Active
-
2016
- 2016-10-25 SA SA516380148A patent/SA516380148B1/ar unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1286708A (zh) * | 1997-12-16 | 2001-03-07 | 拜尔公司 | 聚合物多元醇和稳定剂体系 |
CN1653100A (zh) * | 2002-05-15 | 2005-08-10 | 巴斯福公司 | 通过连续方法制备的接枝多元醇 |
US20130281627A1 (en) * | 2012-04-18 | 2013-10-24 | Bayer Materialscience Llc | Preformed stabilizers useful for the production of polymer polyols and polymer polyols produced therefrom |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020124645A1 (zh) * | 2018-12-21 | 2020-06-25 | 万华化学集团股份有限公司 | 稳定分散剂及其在制备共聚物多元醇中的应用 |
US11945775B2 (en) | 2018-12-21 | 2024-04-02 | Wanhua Chemical Group Co., Ltd. | Stable dispersant and application thereof in preparing copolymer polyols |
CN110283308A (zh) * | 2019-06-21 | 2019-09-27 | 南京金栖化工集团有限公司 | 一种用于合成聚合物多元醇的稳定剂的制备方法 |
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RU2016146798A (ru) | 2018-05-31 |
EP3137527B1 (en) | 2023-11-22 |
KR102475640B1 (ko) | 2022-12-07 |
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US20170051097A1 (en) | 2017-02-23 |
CN110156949B (zh) | 2021-11-23 |
EP3137527A1 (en) | 2017-03-08 |
BR112016024799A2 (pt) | 2017-08-15 |
RU2016146798A3 (zh) | 2018-10-25 |
SA516380148B1 (ar) | 2020-03-22 |
KR20170002477A (ko) | 2017-01-06 |
RU2692255C2 (ru) | 2019-06-24 |
MX2016014227A (es) | 2017-02-14 |
WO2015165878A1 (en) | 2015-11-05 |
CN110156949A (zh) | 2019-08-23 |
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