CN117229490A - Catalyst composition and application thereof, polylactide and preparation method thereof - Google Patents
Catalyst composition and application thereof, polylactide and preparation method thereof Download PDFInfo
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- CN117229490A CN117229490A CN202210632691.1A CN202210632691A CN117229490A CN 117229490 A CN117229490 A CN 117229490A CN 202210632691 A CN202210632691 A CN 202210632691A CN 117229490 A CN117229490 A CN 117229490A
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- containing compound
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- polylactide
- zinc complex
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 61
- -1 alcohol compound Chemical class 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 235000019441 ethanol Nutrition 0.000 claims description 36
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 7
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 6
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 5
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N propoxybenzene Chemical group CCCOC1=CC=CC=C1 DSNYFFJTZPIKFZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 8
- 239000007787 solid Substances 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- 239000003446 ligand Substances 0.000 description 17
- 238000001914 filtration Methods 0.000 description 16
- 238000009826 distribution Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 11
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 10
- 235000019445 benzyl alcohol Nutrition 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229940052810 complex b Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 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 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention relates to the technical field of polymers, and discloses a catalyst composition and application thereof, polylactide and a preparation method thereof. The catalyst composition of the present invention contains at least one metal zinc complex and at least one hydroxyl-containing compound. When the catalyst composition provided by the invention is used for preparing the polylactide by lactide ring-opening polymerization, the catalytic activity is high, the yield is high, and the molecular weight of the obtained polymer is also high.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a catalyst composition and application thereof, and a polylactide and a preparation method thereof.
Background
Polylactic acid (PLA) is a polyester biodegradable material with excellent biodegradability, so that the polylactic acid is widely applied to the manufacture of tableware, films, fibers, clothes, automobile parts and disposable containers, and is beneficial to solving the problem of environmental pollution caused by petrochemical resources. In addition, the polylactic acid has the characteristics of good biocompatibility, no toxicity, degradation adjustability and the like, meets the requirements of medical polymer materials, and has wide application prospects in the aspects of fracture internal and external fixation materials, surgical sutures, tissue engineering scaffold materials, drug slow release and controlled release carrier materials and the like.
The early polyester synthesis method mainly uses the condensation reaction of an acid compound and an alcohol compound, but the structure of a polymer synthesized by the reaction is uncontrollable, and can be a straight chain, branched chain or cyclic structure, the molecular weight distribution is too wide, the molecular weight is low and is not easy to control, and finally the mechanical property of the polymer is poor. In order to improve the comprehensive performance of the polymer, in recent years, the synthesis research of polyester is mainly focused on developing a coordination polymerization catalyst to initiate ring-opening polymerization of cyclic ester to prepare polyester polymer. The method for producing polyesters by ring-opening polymerization has the following advantages compared with the above-mentioned condensation reaction method: first, the molecular weight of the polyester can be precisely controlled, and the molecular weight distribution is narrow; secondly, no water is generated in the process of ring-opening polymerization, so that a polymer with higher molecular weight can be obtained; third, the ring-opening polymerization process can achieve selective polymerization of chiral monomers by selection of a catalyst.
The catalyst system applied to lactone coordination ring-opening polymerization mainly comprises stannous octoate, metallic aluminum, calcium, magnesium, zinc, titanium complex, IIIB group metal complex and the like. Stannous octoate is a catalyst with better effect, has high catalytic activity and small catalyst consumption, can prepare high molecular weight polymer, and has the defects that high-temperature bulk polymerization can be only carried out, and the conversion rate is only about 50% when the molecular weight reaches the highest. To increase the conversion, it is necessary to reduce the molecular weight.
Disclosure of Invention
The invention aims to solve the problems of low catalytic activity and uncontrollable molecular weight in the prior art, and provides a catalyst composition and application thereof, and polylactide and a preparation method thereof. When the catalyst composition provided by the invention is used for preparing the polylactide by lactide ring-opening polymerization, the catalytic activity is high, the yield is high, and the molecular weight of the obtained polymer is also high.
In order to achieve the above object, the present invention provides a catalyst composition comprising at least one metal zinc complex represented by the formula (I) and at least one hydroxyl group-containing compound,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
Preferably, the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:0.5-800.
Preferably, the hydroxyl-containing compound is an alcohol compound and/or a phenolic compound.
Preferably, the hydroxyl group-containing compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, triethanolamine, benzhydrol, tritanol, benzyl alcohol, and phenol.
Preferably, the C 1 -C 6 Alkyl of (2) is methyl, ethyl or propyl.
Preferably, the C 1 -C 6 Alkoxy of (a) is methoxy, ethoxy or propoxy.
Preferably, the halogen is fluorine, chlorine, bromine or iodine.
Preferably, R is methyl, ethyl, propyl, fluoro, chloro, bromo, phenyl, methoxyphenyl, ethoxyphenyl or propoxyphenyl, more preferably methyl, chloro, phenyl, methoxyphenyl or ethoxyphenyl.
In a second aspect, the invention provides the use of the catalyst composition of the invention for the preparation of polylactide.
The third aspect of the present invention provides a method for preparing polylactide, wherein the method comprises: a step of solution-polymerizing a lactide monomer in the presence of at least one metal zinc complex represented by the formula (I) and at least one hydroxyl-containing compound,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
Preferably, the hydroxyl-containing compound is a substituted or unsubstituted C 1 -C 5 Straight-chain or branched fatty alcohols, C 6 -C 10 Aromatic alcohol, C 4 -C 6 At least one of alcohol amine and phenol, and the substituted group is selected from C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy or C 6 -C 10 Aryl groups.
Preferably, the hydroxyl group-containing compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, triethanolamine, benzhydrol, tritanol, benzyl alcohol, and phenol.
Preferably, the C 1 -C 6 Alkyl of (2) is methyl, ethyl or propyl.
Preferably, the C 1 -C 6 Alkoxy of (a) is methoxy, ethoxy or propoxy.
Preferably, the halogen is fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine.
Preferably, R is methyl, ethyl, propyl, fluoro, chloro, bromo, phenyl, methoxyphenyl, ethoxyphenyl or propoxyphenyl, more preferably methyl, chloro, phenyl, methoxyphenyl or ethoxyphenyl.
Preferably, the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:0.5-800.
Preferably, the molar ratio of the hydroxyl group-containing compound to the lactide monomer may be 1:100-16000, more preferably 1:200-15000, more preferably 1:500-5000.
Preferably, the molar ratio of the metal zinc complex represented by formula (I) to the lactide monomer is 1:1-10000, preferably 1:50-5000, more preferably 1:100-2000.
Preferably, the conditions of the solution polymerization include: the reaction temperature is 15-160 ℃, and the reaction time is 0.03-58h.
According to a fourth aspect of the present invention there is provided a polylactide produced by the method of producing a polylactide of the present invention.
Through the technical scheme, the catalyst composition and the application thereof, the polylactide and the preparation method thereof provided by the invention have the following beneficial effects:
the catalyst composition containing the metal zinc complex with the specific structure and the compound containing the hydroxyl can efficiently catalyze lactide ring-opening polymerization reaction under the condition of low metal catalyst concentration, and has high catalytic efficiency, high conversion rate of polymerization reaction and higher molecular weight of the obtained polymer.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalyst composition, wherein the catalyst composition comprises at least one metal zinc complex shown as a formula (I) and at least one compound containing hydroxyl,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
In the present invention, the C 1 -C 6 The alkyl group of (a) means a straight chain alkyl group, branched alkyl group or cycloalkyl group having 1 to 6 carbon atoms.
As said C 1 -C 6 Examples of the alkyl group of (a) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like.
The C is 1 -C 6 The alkoxy group of (a) means a straight chain alkoxy group, branched alkoxy group or cyclic alkoxy group having 1 to 6 carbon atoms.
As said C 1 -C 6 Examples of the alkoxy group include: methoxy, ethoxy, n-propoxy, sec-butoxy, tert-butoxy, pentoxy, n-hexoxy, and the like.
The C is 6 -C 12 The aryl group of (a) means an aryl group having 6 to 12 carbon atoms.
As said C 6 -C 12 Examples of the aryl group of (a) include: phenyl, benzyl, phenethyl, and the like.
According to the present invention, preferably, the C 1 -C 6 Alkyl of (2) is methyl, ethyl or propyl.
According to the present invention, preferably, the C 1 -C 6 Alkoxy of (a) is methoxy, ethoxy or propoxy.
According to the present invention, preferably, the halogen is fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine, still more preferably chlorine.
The R group is preferably as follows: methyl, ethyl, propyl, fluorine, chlorine, bromine, phenyl, methoxyphenyl, ethoxyphenyl or propoxyphenyl, more preferably methyl, chlorine, phenyl, methoxyphenyl or ethoxyphenyl.
According to the invention, the hydroxyl group-containing compound may be an alcohol compound and/or a phenolic compound. Preferably, the hydroxyl-containing compound is a substituted or unsubstituted C 1 -C 5 Straight-chain or branched fatty alcohols, C 6 -C 10 Aromatic alcohol, C 4 -C 6 At least one of alcohol amine and phenol, and the substituted group is selected from C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy or C 6 -C 10 An aryl group; more preferably, the hydroxyl group-containing compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, triethanolamine, benzhydrol, tritanol, benzyl alcohol, and phenol; particularly preferably, the hydroxyl group-containing compound is at least one of isopropyl alcohol, benzyl alcohol, benzhydrol, trityl alcohol and triethanolamine.
According to the present invention, the content of the metal zinc complex and the hydroxyl group-containing compound may vary widely, for example, the molar ratio of the metal zinc complex to the hydroxyl group-containing compound may be 1:0.01-1000, preferably 1:0.5 to 800, more preferably 1:0.5 to 500, further preferably 1:1 to 50, particularly preferably 1:1-10.
According to a second aspect of the present invention there is provided the use of the catalyst composition according to the first aspect of the present invention for the preparation of polylactide.
The two components (namely the metal zinc complex and the hydroxyl-containing compound) in the catalyst composition provided by the invention can be added respectively during the reaction of preparing the polylactide, or can be added simultaneously after being prepared according to the following method: slowly dropwise adding an organic solvent containing the metal zinc complex into an organic solvent containing a compound containing hydroxyl under the conditions of drying and rapid stirring, and vacuum-filtering the obtained mixture to obtain the catalyst composition.
According to a third aspect of the present invention, there is provided a method for preparing polylactide, wherein the method comprises: a step of solution-polymerizing a lactide monomer in the presence of at least one metal zinc complex represented by the formula (I) and at least one hydroxyl-containing compound,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
In the invention, the metal zinc complex is matched with the compound containing hydroxyl, so that the consumption of the metal zinc complex is reduced, a small amount of the metal zinc complex can catalyze and obtain the polylactide with high molecular weight, the catalysis efficiency is high, and the molecular weight of the obtained polymer is also high.
In the present invention, "lactide monomer" means L-lactide, D-lactide, L, D-lactide.
In addition, as for the R group, as described above, description thereof will not be repeated here.
The following is a detailed description of the preparation method of the polylactide of the present invention using a metal zinc complex and a hydroxyl group-containing compound (i.e., the catalyst composition of the present invention).
According to the invention, the amounts of the metal zinc complex and the hydroxyl-containing compound may vary widely, for example, the molar ratio of the metal zinc complex to the hydroxyl-containing compound may be 1:0.01-1000. In order to further improve the catalytic efficiency, preferably, the molar ratio of the metallic zinc complex to the hydroxyl group-containing compound is 1:0.5-800; more preferably, the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:0.5-500; further preferably, the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:1-50; particularly preferably, the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:1-10.
In order to further improve the catalytic efficiency, preferably, the molar ratio of the metal zinc complex represented by formula (I) to the lactide monomer is 1:1-10000, preferably 1:50-5000, more preferably 1:100-2000.
In order to further improve the catalytic efficiency, preferably, the molar ratio of the hydroxyl group-containing compound to the lactide monomer is 1:1-20000, more preferably 1:20-19000, more preferably 1:50-18000, more preferably 1:100-16000, more preferably 1:200-15000, further preferably 1:500-5000.
In the present invention, the manner of adding the metal zinc complex and the hydroxyl group-containing compound is not particularly limited, and may be added separately or simultaneously at the time of the reaction, or may be added simultaneously after having been prepared in advance according to the following method: slowly dropwise adding an organic solvent containing the metal zinc complex into an organic solvent containing a compound containing hydroxyl under the conditions of drying and rapid stirring, and vacuum-filtering the obtained mixture to obtain the catalyst composition.
The organic solvent containing the metal zinc complex and the organic solvent containing the hydroxyl group-containing compound may be the same or different, and preferably the same. Further, as the organic solvent, a solvent used in solution polymerization can be used.
According to the present invention, the solvent used for the solution polymerization may be an organic solvent, preferably at least one of a substituted or unsubstituted alkane, a substituted or unsubstituted benzene, and a substituted or unsubstituted ether.
In a preferred embodiment of the present invention, the solvent is at least one of pentane, hexane, benzene, chlorobenzene, toluene, tetrahydrofuran, diethyl ether, and dichloromethane; more preferably, the solvent is one or more of toluene, tetrahydrofuran and methylene chloride.
According to the present invention, preferably, the conditions of the solution polymerization include: the reaction temperature is 15-160 ℃, and the reaction time is 0.03-58h; more preferably, the conditions of the solution polymerization include: the reaction temperature is 25-100 ℃ and the reaction time is 3-52h. In order to avoid the influence of water, oxygen, and the like on the catalytic activity of the catalyst, the reaction of the present invention is preferably carried out under anhydrous and anaerobic conditions.
And after the reaction is finished, performing post-treatment to obtain the polylactide, wherein the post-treatment comprises the steps of adding the reacted mixed liquid into ethanol solution of hydrochloric acid with the volume concentration of 10v percent to terminate the reaction, then settling the mixed liquid in ethanol, filtering to obtain white solid, and drying the white solid at the temperature of 30-50 ℃ for 36-60 hours to obtain the polylactide.
According to a fourth aspect of the present invention there is provided a polylactide produced by the process for producing a polylactide of the second process of the present invention.
Preferably, the number average molecular weight of the polylactide may be 0.1 to 20 tens of thousands, preferably 0.11 to 15 tens of thousands; the molecular weight distribution is 1-1.5; preferably 1.03-1.3.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the examples below, room temperature is about "25 ℃.
(1) Conversion of polymer: detecting by using a Bruker Avance 400 nuclear magnetic resonance apparatus in Switzerland; the test conditions were: the solvent was deuterated chloroform and the test temperature was room temperature.
(2) Molecular weight and distribution of the polymer: measured by using a liquid phase Gel Permeation Chromatograph (GPC) of Shimadzu LC-20A type; the test conditions were: the solvent was chloroform at a test temperature of 25℃and a flow rate of 1mL/min.
(3) Elemental analysis (for metal complexes): measured by using a Elementar Vario EL type elemental analyzer.
The ligand structure used in the embodiment of the invention is shown in the following formula (II), and the preparation method is as follows:
weighing the molar ratio of 1:2 and the compound with the structure shown in the formula (II-1) are respectively dissolved in absolute ethyl alcohol, the temperature is raised to 55 ℃ for reaction for 5 hours after uniform mixing, cooling is carried out, a large amount of precipitate is separated out, the solution is washed by absolute ethyl alcohol for 3 times, and the solution is dried and stored in vacuum for standby.
Wherein,
ligand A (formula (II), R is phenyl) of formula C 52 H 40 N 6 O 2 (actual measurement value): c,79.59 (79.58); h,5.10 (5.12); n,10.71 (10.70); o,4.08 (4.09).
Ligand B (formula (II), R is chlorine) of formula C 40 H 30 Cl 2 N 6 O 2 (actual measurement value): c,68.97 (68.95); h,4.31 (4.32); n,12.07 (12.06); o,4.60 (4.61).
Ligand C (formula (II), R is methoxyphenyl) with molecular formula C 54 H 44 N 6 O 4 (actual measurement value): c,77.14 (77.12); h,5.24 (5.26); n,10.00 (9.97); o,7.62 (7.63).
Ligand D (formula (II) wherein R is methyl) having the formula C 42 H 36 N 6 O 2 (actual measurement value): c,76.83 (76.82); h,5.49 (5.51); n,12.80 (12.78); o,4.88 (4.89).
Preparation example 1
Preparation of metallic Zinc Complex A (in formula (I), R is phenyl)
A ligand a having a structure as shown in formula (II), wherein R is phenyl. 1.0mmol of Zn (CH) 3 COO) 2 ·nH 2 The acetonitrile and methanol (1:1) solution of the O ligand was added dropwise to 20ml of acetonitrile and methanol (1:1) solution containing an equivalent amount of ligand A, stirred at room temperature for 2 hours, 3ml of DMF was added dropwise, filtered to give a pale yellow clear solution, evaporated at room temperature, filtered, and dried under vacuum to give a metal zinc complex A in a yield of 42%.
Elemental analysis data for the product were: c (C) 52 H 40 N 6 O 2 Zn (actual measurement value): c,73.50 (73.49); h,4.71 (4.72); n,9.89 (9.87); o,3.77 (3.78).
Preparation example 2
Preparation of metallic Zinc Complex B (in formula (I), R is chlorine)
Ligand A having a structure as shown in formula (II), wherein R is chlorine. 1.0mmol of Zn (C) was dissolvedH 3 COO) 2 ·nH 2 The acetonitrile and methanol (1:1) solution of the O ligand was added dropwise to 20ml of acetonitrile and methanol (1:1) solution containing an equivalent amount of ligand A, stirred at room temperature for 2 hours, 3ml of DMF was added dropwise, and filtration was performed to obtain a pale yellow clear solution, which was volatilized at room temperature, filtered, and dried under vacuum to obtain a metal zinc complex A, the yield of which was 43%.
Elemental analysis data for the product were: c (C) 40 H 30 Cl 2 N 6 O 2 Zn (actual measurement value): c,63.07 (63.05); h,3.94 (3.95); n,11.04 (11.04); o,4.20 (4.21).
Preparation example 3
Preparation of metallic Zinc Complex C (in formula (I), R is methoxyphenyl)
A ligand a having a structure as shown in formula (II), wherein R is methoxyphenyl. 1.0mmol of Zn (CH) 3 COO) 2 ·nH 2 The acetonitrile and methanol (1:1) solution of the O ligand was added dropwise to 20ml of acetonitrile and methanol (1:1) solution containing an equivalent amount of ligand A, stirred at room temperature for 2 hours, 3ml of DMF was added dropwise, filtered to give a pale yellow clear solution, evaporated at room temperature, filtered, and dried under vacuum to give a metallic zinc complex A in 40% yield.
Elemental analysis data for the product were: c (C) 54 H 44 N 6 O 4 Zn (actual measurement value): c,71.60 (71.60); h,4.86 (4.87); n,9.28 (9.27); o,7.07 (7.07).
Preparation example 4
Preparation of metallic Zinc Complex D (in formula (I), R is methyl)
A ligand a having a structure as shown in formula (II), wherein R is methyl. 1.0mmol of Zn (CH) 3 COO) 2 ·nH 2 The acetonitrile and methanol (1:1) solution of the O ligand was added dropwise to 20ml of acetonitrile and methanol (1:1) solution containing an equivalent amount of ligand A, stirred at room temperature for 2 hours, 3ml of DMF was added dropwise, and filtration was performed to obtain a pale yellow clear solution, which was volatilized at room temperature, filtered, and dried under vacuum to obtain a metal zinc complex A, the yield of which was 41%.
Elemental analysis data for the product were: c (C) 42 H 36 N 6 O 2 Zn (actual measurement value): c,69.90 (69.91); h,4.99 (5.01); n,11.65 (11.64); o,4.44 (4.45).
Example 1
At room temperature, 10 mu mol of metal zinc complex A, 10 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 40mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 70 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 93% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 0.41 ten thousand of a molecular weight distribution M w /M n 1.26.
Example 2
At room temperature, 10 mu mol of metal zinc complex A, 10 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 20mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, white solid is obtained by filtration, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 94% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 0.51 ten thousand, molecular weight distribution M w /M n 1.26.
Example 3
At room temperature, 10 mu mol of metal zinc complex B, 10 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 10mmol of L, D-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 96% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 12.3 ten thousand of molecular weight distribution M w /M n 1.19.
Example 4
At room temperature, 10 mu mol of metal zinc complex C, 100 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 10mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 97% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 5.7 ten thousand, molecular weight distribution M w /M n 1.17.
Example 5
At room temperature, 10 mu mol of metal zinc complex C, 10 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 5mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 94% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 7.9 ten thousand of molecular weight distribution M w /M n 1.22.
Example 6
At room temperature, 10 mu mol of metal zinc complex B, 200 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 10mmol of L, D-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 96% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 0.81 ten thousand of molecular weight distribution M w /M n 1.11.
Example 7
At room temperature, 10 mu mol of metal zinc complex D, 500 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 10mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 98% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 0.49 ten thousand, molecular weight distribution M w /M n 1.12.
Example 8
At room temperature, 10 mu mol of metal zinc complex A, 10 mu mol of benzyl alcohol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 1mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 91% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 1.51 ten thousand of molecular weight distribution M w /M n 1.26.
Example 9
At room temperature, 10 mu mol of metal zinc complex D, 10 mu mol of isopropanol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 10mmol of L-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction solution is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 94% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 10.5 ten thousand of the molecular weight distribution M w /M n 1.23.
Example 10
At room temperature, 10 mu mol of metal zinc complex D, 0.5 mu mol of benzyl alcohol, 0.5 mu mol of benzhydrol and 10mL of toluene solvent are added into a 20mL anhydrous and anaerobic polymerization bottle, 5mmol of D-lactide monomer is added, stirring reaction is carried out for 48 hours at 100 ℃, then ethanol solution of hydrochloric acid with volume concentration of 10v% is added for stopping reaction, reaction liquid is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 92% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 5.9 ten thousand, molecular weight distribution M w /M n 1.25.
Comparative example 1
At room temperature, 10 mu mol of metal zinc complex A and 10mL of toluene solvent are added into a 20mL polymerization bottle which is subjected to anhydrous and anaerobic treatment, 1mmol of L-lactide monomer is added, stirring reaction is carried out at 100 ℃ for 48 hours, then ethanol solution of hydrochloric acid with the volume concentration of 10v% is added for stopping the reaction, the reaction liquid is poured into ethanol for sedimentation, filtration is carried out to obtain white solid, and the white solid is dried in a vacuum drying box at 40 ℃ for 48 hours to obtain polylactide solid.
The conversion was 65% by nuclear magnetic resonance test.
GPC analysis of number average molecular weight M of polylactide n 0.43 ten thousand, molecular weight distribution M w /M n 1.28.
Comparative example 2
And (3) at 180 ℃, mixing 25mmol L-lactide monomer with 6 mu mol stannous octoate, performing melt polymerization, stopping the reaction after the reaction is performed for 90 minutes, cooling, placing the obtained product in a vacuum drying oven, and drying at 40 ℃ for 48 hours to obtain the polylactide solid.
The conversion rate of the nuclear magnetic test is 92%.
Analysis of the number average molecular weight M of the polylactide by GPC n =7.8 million, mw/mn=1.67.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A catalyst composition comprising at least one metal zinc complex of formula (I) and at least one hydroxyl-containing compound,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
2. The catalyst composition of claim 1, wherein the molar ratio of the metal zinc complex to the hydroxyl-containing compound is 1:0.5-800.
3. The catalyst composition of claim 1, wherein the hydroxyl-containing compound is an alcohol compound and/or a phenolic compound;
preferably, the hydroxyl group-containing compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, triethanolamine, benzhydrol, tritanol, benzyl alcohol, and phenol.
4. A catalyst composition according to any one of claims 1 to 3, wherein the C 1 -C 6 Alkyl of (2) is methyl, ethyl or propyl;
preferably, the C 1 -C 6 Alkoxy of (a) is methoxy, ethoxy or propoxy;
preferably, the halogen is fluorine, chlorine, bromine or iodine;
preferably, R is methyl, ethyl, propyl, fluoro, chloro, bromo, phenyl, methoxyphenyl, ethoxyphenyl or propoxyphenyl, more preferably methyl, chloro, phenyl, methoxyphenyl or ethoxyphenyl.
5. Use of the catalyst composition according to any of claims 1-4 for the preparation of polylactide.
6. A method for preparing polylactide, which is characterized by comprising the following steps: a step of solution-polymerizing a lactide monomer in the presence of at least one metal zinc complex represented by the formula (I) and at least one hydroxyl-containing compound,
in the formula (I), R is C 1 -C 6 Alkyl, halogen, C 6 -C 12 Or the hydrogen atom on the aryl is selected from halogen, C 1 -C 6 Alkyl and C of (C) 1 -C 6 C substituted by at least one group in the alkoxy group of (C) 6 -C 12 Aryl groups of (a).
7. The method of claim 6, wherein the hydroxyl-containing compound is a substituted or unsubstituted C 1 -C 5 Straight-chain or branched fatty alcohols, C 6 -C 10 Aromatic alcohol, C 4 -C 6 At least one of alcohol amine and phenol, and the substituted group is selected from C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy or C 6 -C 10 An aryl group;
preferably, the hydroxyl group-containing compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, triethanolamine, benzhydrol, tritanol, benzyl alcohol, and phenol.
8. The method of claim 6, wherein the C 1 -C 6 Alkyl of (2) is methyl, ethyl or propyl;
preferably, the C 1 -C 6 Alkoxy of (a) is methoxy, ethoxy or propoxy;
preferably, the halogen is fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine;
preferably, R is methyl, ethyl, propyl, fluoro, chloro, bromo, phenyl, methoxyphenyl, ethoxyphenyl or propoxyphenyl, more preferably methyl, chloro, phenyl, methoxyphenyl or ethoxyphenyl.
9. The method of any of claims 6-8, wherein the molar ratio of the metallic zinc complex to the hydroxyl-containing compound is 1:0.5-800;
preferably, the molar ratio of the hydroxyl group-containing compound to the lactide monomer may be 1:100-16000, more preferably 1:200-15000, more preferably 1:500-5000;
preferably, the molar ratio of the metal zinc complex represented by formula (I) to the lactide monomer is 1:1-10000, preferably 1:50-5000, more preferably 1:100-2000.
10. The method of any of claims 6-8, wherein the conditions of the solution polymerization comprise: the reaction temperature is 15-160 ℃, and the reaction time is 0.03-58h.
11. The polylactide prepared by the method of any one of claims 6-10.
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