CN113754535A - Method for catalyzing and depolymerizing polylactic acid and analogue thereof by magnesium catalysis system - Google Patents
Method for catalyzing and depolymerizing polylactic acid and analogue thereof by magnesium catalysis system Download PDFInfo
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- CN113754535A CN113754535A CN202111052518.6A CN202111052518A CN113754535A CN 113754535 A CN113754535 A CN 113754535A CN 202111052518 A CN202111052518 A CN 202111052518A CN 113754535 A CN113754535 A CN 113754535A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 43
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 39
- 239000011777 magnesium Substances 0.000 title claims abstract description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- -1 bis (hexamethyldisilazane) magnesium Chemical compound 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229950009195 phenylpropanol Drugs 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 11
- 229920000728 polyester Polymers 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 64
- 229920000642 polymer Polymers 0.000 description 26
- 238000001514 detection method Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 12
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical group CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 12
- 229940057867 methyl lactate Drugs 0.000 description 12
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 9
- 229940116333 ethyl lactate Drugs 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOSNYUDSMPILKL-UHFFFAOYSA-N Methyl DL-Leucate Chemical group COC(=O)C(O)CC(C)C JOSNYUDSMPILKL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- HBOGUIFRIAXYNB-UHFFFAOYSA-N ethyl 2-hydroxy-3-phenylpropanoate Chemical group CCOC(=O)C(O)CC1=CC=CC=C1 HBOGUIFRIAXYNB-UHFFFAOYSA-N 0.000 description 1
- KWWOQRSLYPHAMK-UHFFFAOYSA-N ethyl 2-hydroxybutanoate Chemical group CCOC(=O)C(O)CC KWWOQRSLYPHAMK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical group COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- OQXGUAUSWWFHOM-UHFFFAOYSA-N methyl 2-hydroxy-3-methylpentanoate Chemical group CCC(C)C(O)C(=O)OC OQXGUAUSWWFHOM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for catalyzing and depolymerizing polylactic acid and an analogue thereof by a magnesium catalysis system, belonging to the technical field of polyester depolymerization. The invention realizes alcoholysis of polylactic acid and analogues thereof under the catalysis of bis (hexamethyldisilazane) magnesium or dibutyl magnesium catalyst and the participation of alcohol compounds to obtain organic micromolecules, thereby realizing effective utilization of the waste polylactic acid and analogues thereof. The catalyst has good universality, and has good depolymerization effect on polylactic acid and similar materials with various different structures.
Description
Technical Field
The invention relates to a method for catalyzing and depolymerizing polylactic acid and an analogue thereof by a magnesium catalysis system, belonging to the technical field of polyester depolymerization.
Background
Aliphatic polyester-based biomass materials, which are perfect substitutes for petroleum-derived materials, can be produced by biological photosynthesis from carbon dioxide, water and sunlight available in the atmosphere, have been used for the production of fuels and fine chemicals with the goal of achieving zero net carbon emissions. Polyester materials are widely used in packaging materials and pharmaceutical industry due to their biocompatibility and degradability, particularly polylactic acid materials. And therefore has received increasing attention worldwide. However, mass production of polylactic acid materials also raises concerns about post-treatment of waste polyester. Although polylactic acid, as a degradable polymer, is capable of degrading into carbon dioxide and water, this usually requires certain harsh environmental conditions and is time consuming. The method for efficiently and conveniently realizing the post-treatment of the polylactic acid material is an environmental problem which needs to be solved at present.
At present, the methods for recycling the polymer mainly comprise high-temperature pyrolysis, hydrolysis, an enzymolysis method and the like. However, pyrolysis and hydrolysis usually require high temperature, so that more energy is consumed, and the operation cost is increased; the enzymolysis method has specificity, can only depolymerize certain specific polyester materials, and has certain limitation. Another chemical recycling method is to alcoholyze the polyester into small organic molecules by transesterification with alcohol. The method can realize depolymerization of the polymer and complete post-treatment of the waste polymer, and simultaneously, the generated alcoholysis product is effectively utilized as a useful chemical so as to change the waste polymer into valuables, and the method conforms to the principle of sustainable development, thereby having important research significance.
There are only few reports on transesterification and alcoholysis of polylactic acid. Enthaler et al reported a method of depolymerisation of polylactide using stannous octoate catalysis (Polymer. chem., 2020, 11, 2625-2629) by microwave heating to 160 ℃ in the presence of methanol to depolymerise the polylactide to methyl lactate. However, metallic tin has some toxicity, and the high temperature condition causes the production cost to be increased.
Therefore, for the post-treatment of the waste polyester material, the cyclic utilization of the polymer through alcoholysis has a plurality of advantages, but a simple, efficient, green and environment-friendly catalytic system is urgently needed, so that the depolymerization of the polyester material can be rapidly realized under mild conditions. This is of great significance for environmental protection and sustainable development.
Disclosure of Invention
The invention provides a method for catalyzing and depolymerizing polylactic acid and analogues thereof by using a magnesium catalytic system, aiming at solving the technical problems in the prior art.
The technical scheme of the invention is as follows:
a process for preparing the polylactic acid or its analog by catalytic depolymerizing in Mg-catalyst system includes such steps as polymerizing under the protection of inertial gas and at a certain temp and under the condition of organic solvent or no solvent in bis (hexamethyldisilazane) Mg [ N (SiMe)3)2]2Or dibutyl magnesium MgBu2The polymerization unit is catalyzed and depolymerized in alcohol compounds under the catalysis of a catalyst.
Further defined, the polymerized units are one or more of the following structures:
wherein R is1、R2Is hydrogen, alkyl, alkoxy, aryl or halogen atom, and n is 1 or more.
Further defined, the number average molecular weight of the polymerized units is 102～107g/mol。
Further, the alcohol compound is one or more of C1-C50 alcohol and is mixed in any proportion.
Further, the alcohol compound is one or more of methanol, ethanol, isopropanol, butanol, tert-butanol, benzyl alcohol, and phenylpropanol, and is mixed at any ratio.
More particularly, the alcohol compound is methanol.
Further limit, the organic solvent is one or more than two of benzene, toluene, xylene, dichloromethane and tetrahydrofuran which are mixed in any proportion.
Further, the amount of the catalyst added is 0.1 to 10 wt% based on the polymerization unit.
Further limiting, the temperature is 20-200 ℃.
Further defined, the inert gas is argon or nitrogen.
The invention has the following beneficial effects:
(1) the catalyst adopted by the invention is a bis (hexamethyldisilazane) magnesium or dibutyl magnesium catalyst with simple and green structure, and can depolymerize polylactic acid and analogues thereof into small organic molecules under mild conditions through ester exchange reaction catalyzed by the catalyst in the presence of alcohol compounds, thereby realizing reutilization of the waste polylactic acid and conforming to the principle of sustainable development.
(2) The invention adopts the magnesium catalyst with simple structure to catalyze the depolymerization of polylactic acid and the like, and the magnesium metal is nontoxic, colorless, cheap and easy to obtain, has good biocompatibility, and ensures that the production process is more green and environment-friendly; and the catalyst has a simple structure and few synthesis steps, so that the production cost is more economic.
(3) The catalytic system adopted by the invention has good universality and good depolymerization effect on polylactic acid and analogues thereof with various structures.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a depolymerization product of polylactic acid of example 2;
FIG. 2 shows the states of the respective stages in the depolymerization process of polylactic acid in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and then 288mg of polylactic acid (M) was added to the flaskn26000g/mol, PDI 1.09), then 3.8Mg of Mg [ N (SiMe) is added3)2]2The catalyst was added to 2mL of methanol and 2mL of methylene chloride outside the glove box, and the mixture was stirred at room temperature to react. After the reaction is carried out for 1.5h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is methyl lactate.
Example 2:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a500 mL three-necked flask was taken, vacuum-baked and purged with argon, and then 16.32g of a commercial polylactic acid product (manufacturer: Nigaku, Shuangtong Daiki Co., Ltd.; diameter: 12mm) was put into a glove box, followed by 1.15g of Mg [ N (SiMe)3)2]2113mL of methanol and 113mL of methylene chloride were added to the outside of the glove box as a catalyst, and the reaction was stirred at room temperature. After reacting for 2 hours, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is methyl lactate. The remaining methanol was removed by distillation to obtain 20.84g of methyl lactate in 80% yield.
Example 3:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged with 144mg of polylactic acid (M) in a glove box after evacuating and replacing argon gasn11300g/mol, PDI 1.17), then 7.0Mg of Mg [ N (SiMe) was added3)2]2The catalyst is arranged outside the glove box,1mL of methanol was added, and the reaction was stirred at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is methyl lactate.
Example 4:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a50 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 11.0g of polylactic acid (M) was added to the flaskn49900g/mol, PDI 1.13), and then 492Mg of Mg [ N (SiMe)3)2]2And adding 30mL of methanol outside the glove box, and stirring at normal temperature for reaction. After reacting for 40 minutes, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is methyl lactate. The remaining methanol was removed by distillation to obtain 14.2g of methyl lactate in 92% yield.
Example 5:
depolymerization of polyethylglycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and 86mg of polyethylglycolide (M) was added to the flaskn10337g/mol, PDI 1.26) and then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy methyl butyrate.
Example 6:
depolymerization of polyisopropylglycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of poly (isopropyl glycolide) (M) was added to the flaskn10700g/mol, PDI 1.22), then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy-3-methyl butyric acid methyl ester.
Example 7:
depolymerization of poly (propylglycolide)
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of poly (propylglycolide) (M) was added to the flaskn10780g/mol, PDI 1.17), then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy methyl valerate.
Example 8:
depolymerization of polybutyl glycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of polybutylglycolide (M) was added to the flaskn11400g/mol, PDI 1.32), then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. Reaction 2After h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy methyl caproate.
Example 9:
depolymerization of polyisobutylglycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of polyisobutylglycolide (M) was added into the glove boxn12000g/mol, PDI 1.21), then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After 4 hours of reaction, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy-4-methyl pentanoic acid methyl ester.
Example 10:
depolymerization of poly-sec-butyl glycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of poly-sec-butylglycolide (M) was added to the flaskn13200g/mol, PDI 1.28), then 3.5Mg of Mg [ N (SiMe) is added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After 5h of reaction, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is 2-hydroxy-3-methyl pentanoic acid methyl ester.
Example 11:
depolymerization of poly (benzyl glycolide)
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged with 148mg of poly (benzylglycolide) (M) in a glove box after evacuating and replacing argon gasn9200g/mol, PDI 1.22), then 3.5Mg of Mg [ N (SiMe) is added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is benzyl methyl lactate.
Example 12:
depolymerization of poly (benzylethyl glycolide)
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and then 160mg of poly (benzylethyl glycolide) (M) was added to the flaskn9500g/mol, PDI 1.21), then 3.5Mg of Mg [ N (SiMe) was added3)2]2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is benzyl ethyl methyl lactate.
Example 13:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and then 288mg of polylactic acid (M) was added to the flaskn26.0kg/mol, PDI 1.09), then 3.8Mg of Mg [ N (SiMe) was added3)2]2The catalyst was added to 2mL of ethanol and 2mL of methylene chloride outside the glove box, and the mixture was stirred at room temperature to react. After reacting for 2h, detecting the reaction system by nuclear magnetism, wherein the conversion rate of the polymer is 98 percent, and obtainingThe alcoholysis product is ethyl lactate.
Example 14:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a500 mL three-neck flask was taken, vacuum-baked and replaced with argon, and then 15g of a commercial polylactic acid product (manufacturer: Henxin environmental protection technologies, Inc.; model: BG73) was added to the flask, followed by 1.15g of Mg [ N (SiMe)3)2]2113mL of ethanol and 113mL of methylene chloride were added to the outside of the glove box as a catalyst, and the reaction was stirred at room temperature. After reacting for 2 hours, detecting the reaction system by nuclear magnetism, wherein the conversion rate of the polymer is 99 percent, and the obtained alcoholysis product is ethyl lactate. The remaining ethanol was removed by distillation to obtain 18.3g of ethyl lactate with a yield of 85%.
Example 15:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and then 144mg of polylactide (M) was added into the glove boxn11300g/mol, PDI 1.17), then 7.0Mg of Mg [ N (SiMe) was added3)2]2And adding 1mL of ethanol outside the glove box, and stirring at normal temperature for reaction. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is ethyl lactate.
Example 16:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a50 mL Schlenk flask was evacuated and purged with argon, and then 12.0g of polylactide (M) was added to the flaskn49900g/mol, PDI 1.13), followed by 495Mg of Mg [ N (SiMe) added3)2]2And adding 30mL of ethanol outside the glove box as a catalyst, and stirring at normal temperature for reaction. After reacting for 1h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is ethyl lactate. The remaining ethanol was removed by distillation to obtain 15.3g of ethyl lactate with a yield of 88%.
Example 17:
depolymerization of polyethylglycolide
The experimental process comprises the following steps:
a5 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 100mg of polyethylglycolide (M) was added to the flaskn10337g/mol, PDI 1.26) and then 3.5Mg of Mg [ N (SiMe) was added3)2]2And adding 1mL of ethanol outside the glove box, and stirring at normal temperature for reaction. After reacting for 2h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is ethyl 2-hydroxybutyrate.
Example 18:
depolymerization of poly (benzyl glycolide)
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and 150mg of poly (benzylglycolide) (M) was added to the flaskn9200g/mol, PDI 1.22), then 3.5Mg of Mg [ N (SiMe) is added3)2]2And adding 1mL of ethanol outside the glove box, and stirring at normal temperature for reaction. After 5h reaction, the reaction was checked by nuclear magnetic resonanceIn the system, the conversion rate of the polymer is 99 percent, and the obtained alcoholysis product is ethyl phenyl lactate.
Example 19:
depolymerization of polylactic acid
The experimental process comprises the following steps:
a50 mL Schlenk flask was taken, vacuum-baked and purged with argon, and then 11.0g of polylactic acid (M) was added to the flaskn49900g/mol, PDI 1.13), and then 220mg of MgBu is added2And adding 30mL of methanol outside the glove box, and stirring at normal temperature for reaction. After reacting for 50 minutes, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is methyl lactate. The remaining methanol was removed by distillation to obtain 13.2g of methyl lactate with a yield of 86%.
Example 20:
depolymerization of poly (benzyl glycolide)
The experimental process comprises the following steps:
a5 mL Schlenk flask was charged, vacuum-baked, and purged with argon, and 150mg of poly (benzylglycolide) (M) was added to the flaskn9700g/mol, PDI 1.12), then 1.4mg of MgBu is added2Catalyst, add 1mL methanol outside the glove box, stir reaction at room temperature. After reacting for 3h, nuclear magnetic detection is carried out on the reaction system, the conversion rate of the polymer is 99%, and the obtained alcoholysis product is benzyl methyl lactate.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for catalytic depolymerization of polylactic acid and its analogues by magnesium catalytic system features that under normal pressure and protection of inertial gas and at a certain temp, the polylactic acid or its analogues is used as polymerizing unit, and under the condition of organic solvent or no solvent, magnesium Mg [ N (SiMe) is added3)2]2Or dibutyl magnesium MgBu2The polymerization unit is catalyzed and depolymerized in alcohol compounds under the catalysis of a catalyst.
2. The method of claim 1, wherein the polymerization unit is one or more of the following structures:
wherein R is1、R2Is hydrogen, alkyl, alkoxy, aryl or halogen atom, and n is 1 or more.
3. The method of claim 1, wherein the number average molecular weight of the polymeric unit is 102～107g/mol。
4. The method of claim 1, wherein the alcohol compound is one or more than two of C1-C50 alcohols mixed at any ratio.
5. The method of claim 4, wherein the alcohol compound is one or more of methanol, ethanol, isopropanol, butanol, tert-butanol, benzyl alcohol, and phenylpropanol, and is mixed at any ratio.
6. The method of claim 1 or 4, wherein the alcohol compound is methanol.
7. The method of claim 1, wherein the organic solvent is one or more of benzene, toluene, xylene, dichloromethane and tetrahydrofuran, and is mixed at any ratio.
8. The method for controllably depolymerizing polylactic acid and analogues thereof by using the magnesium catalyst system according to claim 1, wherein the amount of the catalyst is 0.1-10 wt% of the polymerization unit.
9. The method of claim 1, wherein the temperature is 20-200 ℃.
10. The method of claim 1, wherein the inert gas is argon or nitrogen.
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