CN115073418B - Zinc complex catalyst and method for depolymerizing high-regularity polylactic acid and recycling racemic lactide - Google Patents

Zinc complex catalyst and method for depolymerizing high-regularity polylactic acid and recycling racemic lactide Download PDF

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CN115073418B
CN115073418B CN202210890799.0A CN202210890799A CN115073418B CN 115073418 B CN115073418 B CN 115073418B CN 202210890799 A CN202210890799 A CN 202210890799A CN 115073418 B CN115073418 B CN 115073418B
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polylactic acid
regularity
lactide
depolymerizing
zinc
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CN115073418A (en
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王庆刚
徐广强
苏家丰
杨茹琳
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

The invention discloses a magnesium catalyst and a method for depolymerizing high-regularity polylactic acid to recover racemized lactide, belonging to the technical field of high-regularity polylactic acid degradation. The invention solves the problems that the prior polylactic acid is mostly PLLA for degradation and the polylactic acid with high tacticity is lack of degradation. According to the invention, the zinc complex catalyst prepared from the inorganic zinc compound and the 1, 10-phenanthroline in situ is adopted to catalyze and degrade the polylactic acid with high regularity under the conditions of high temperature and high vacuum degree, so that the recycling of the waste polylactic acid with the regularity higher than 85% is realized. The zinc complex catalyst adopted by the invention can be prepared in situ only in the depolymerization process, so that the production cost is more economic, and the catalyst is suitable for mass production.

Description

Zinc complex catalyst and method for depolymerizing high-regularity polylactic acid and recycling racemic lactide
Technical Field
The invention relates to a zinc complex catalyst and a method for depolymerizing high-regularity polylactic acid to recover racemized lactide, belonging to the technical field of high-regularity polylactic acid degradation.
Background
The most important of petroleum compounds is plastics, which are the largest synthetic consumer products in the world, but petroleum resources are limited and not renewable, one of the targets is to find out substitutes of the existing plastics, and the biomass material of aliphatic polyesters is long as substitutes of petroleum derived materials, wherein the polylactic acid materials are derived from natural corns, the corn is widely planted, the yield is stable, and the polylactic acid materials belong to completely biodegradable environment-friendly materials, can be naturally decomposed into carbon dioxide and water in nature through the action of microorganisms in nature, and are expected to become substitutes of the traditional petroleum-based source plastics.
The present study shows that the main chain structure of polylactic acid, especially the tacticity, has important influence on the performance, and the polylactic acid is prepared from L-lactide L-LAThe obtained L-polylactic acid PLLA is a polylactic acid material which is widely applied at present, and the polylactic acid is used as a semi-crystalline polymer and has a melting point of 160-170 ℃. In order to further obtain polylactic acid materials with higher performance, a great deal of researches on polylactic acid with high tacticity are carried out at present, the polylactic acid with high tacticity is prepared by ring-opening polymerization of racemic lactide under the catalysis of a catalyst with stereoselectivity, and the polylactic acid has some properties different from PLLA due to the interaction of poly-L-polylactic acid with long blocks and poly-D-polylactic acid in molecular chains, such as a melting point 30-60 ℃ higher than that of PLLA, and also has higher mechanical strength. On the other hand, the use of racemic lactide as a polymerization monomer reduces the process of purifying the monomer to obtain levorotatory lactide with high optical purity, so that polylactic acid with high regularity has been greatly developed. As Li Zhibo, the ring-opening polymerization of racemic lactide catalyzed by CTPB is reportedP m Can reach 0.93, the melting point can reach 183 ℃, and is 167 ℃ higher than the PLLA under the same molecular weightACS Macro Lett.2018,7, 624-628). Jincai Ring-opening polymerization of racemic lactide catalyzed by crown ether-assisted metallic potassium complexP m Up to 0.94 and the melting point up to 192 DEG CInorg. Chem.2016,55, 1, 136–143）。
The polylactic acid with high tacticity is greatly developed, and meanwhile, the recycling of waste is also focused based on the principle of sustainable development. Although a series of researches on depolymerization of polylactic acid are reported at present, the research on depolymerization of PLLA is focused, and recycling of polylactic acid with high tacticity is not researched. Therefore, for discarding the high-regularity polylactic acid material, a method capable of rapidly realizing the directional depolymerization of the high-regularity polylactic acid material is needed.
Disclosure of Invention
The invention provides a zinc-based complex catalyst and a method for depolymerizing high-regularity polylactic acid to recover racemic lactide, which aims to solve the problem that most of the existing polylactic acid degradation is PLLA and lacks of high-regularity polylactic acid degradation.
The technical scheme of the invention is as follows:
the invention aims at providing a method for depolymerizing high-regularity polylactic acid, which comprises the following steps: under the conditions of high temperature and vacuum, catalyzing and depolymerizing the polylactic acid with high regularity by using a zinc complex catalyst to obtain lactide, wherein the polylactic acid with high regularityPm= 0.85～1.0。
Further defined, the zinc complex catalyst is prepared in situ by directly adding 1, 10-phenanthroline and a metallic zinc compound into a depolymerization reaction system.
Further defined, the metallic zinc compound is zinc chloride or zinc acetate.
Further limited, the addition amount of the zinc complex is 0.01 wt% -20 wt% of the polylactic acid with high regularity.
Further, the high temperature is 30 to 300 ℃.
Further defined, the vacuum conditions are between 0.001mbar and 100mbar.
Further defined, the high-regularity polylactic acid has a number average molecular weight of 10 2 g/mol～10 7 g/mol。
Further defined, the L-configuration content in the high-regularity polylactic acid is 1% -100%.
Further defined, the polymeric units of the highly regular polylactic acid have the following structure:
wherein x and y represent the content of L-form and D-form in the highly regular polylactic acid, respectively.
Further defined, the proportion of meso-lactide is 2% to 10%.
According to the invention, the zinc complex catalyst prepared from the inorganic zinc compound and the 1, 10-phenanthroline in situ is adopted to catalyze and degrade the polylactic acid with high regularity under the conditions of high temperature and high vacuum degree, so that the recycling of the waste polylactic acid with the regularity higher than 85% is realized. Compared with the prior art, the application has the following beneficial effects:
(1) The method adopts the zinc complex to catalyze the polylactic acid with high regularity, and the catalyst only needs to be prepared in situ in the depolymerization process, so that the production cost is more economic.
(2) The content of L-LA and D-LA in the product obtained by the catalytic degradation of polylactic acid depends on the ratio of the two polylactic acids with high regularity.
(3) The polylactic acid degraded by the method is high-regularity polylactic acid, fills the gap of high-regularity polylactic acid catalytic degradation, and provides more possibility for the application of the polylactic acid.
(4) The high-regularity polylactic acid degradation process provided by the invention is simple and is suitable for large-scale production.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a product obtained by depolymerizing highly regular polylactic acid in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Example 1:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then adding 95 mg ZnCl 2 And an equimolar amount of 1, 10-phenanthroline, heated to 2After 4 h was distilled under reduced pressure at 20℃and 1mbar, 98% yield was obtained by weighing and the lactide was verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the proportion of racemic lactide was 95% and the proportion of meso-lactide was 5%.
Example 2:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then 190 mg ZnCl is added 2 And equimolar amounts of 1, 10-phenanthroline, heating to 220 ℃, distilling under reduced pressure at a pressure of 1mbar to react 5 h, and weighing to obtain a product lactide with a yield of 97%, which is verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy (as shown in fig. 1), and wherein the proportion of racemic lactide is 91% and the proportion of meso-lactide is 9%.
Example 3:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then Zn (OAc) of 127 mg was added 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, and distilling under reduced pressure at a pressure of 1mbar to obtain the product lactide with a yield of 96% verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy by weighing, wherein the proportion of racemic lactide is 96%, and the proportion of meso-lactide is 4%.
Example 4:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then 254 mg Zn (OAc) was added 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, distilling under reduced pressure at a pressure of 1mbar for reaction of 5 h, and weighing to obtain the product lactide with a yield of 97% verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the proportion of racemic lactide is 95%, and the proportion of meso-lactide is 5%.
Example 5:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 99%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, distilling under reduced pressure at a pressure of 1mbar for 4 h, weighing to obtain yield of 97%, and verifying that the product is lactide by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the ratio of L-LA is 95%, and the ratio of D-LA is<0.5% of meso-lactide, 5%.
Example 6:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 1%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, distilling under reduced pressure at a pressure of 1mbar for 4 h, and weighing to obtain lactide product with yield of 94% and verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the ratio of L-LA is<0.5%, 94% of D-LA and 6% of meso-lactide.
Example 7:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, and distilling under reduced pressure at the pressure of 0.07 mbar to obtain the product with the yield of 95% by weighing, wherein the product is verified to be lactide by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, and the proportion of racemic lactide is 92% and the proportion of meso-lactide is 8%.
Example 8:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 180 ℃, and distilling under reduced pressure at the pressure of 0.07 mbar to obtain the product lactide with the yield of 93 percent and verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy by weighing, wherein the proportion of racemic lactide is 93 percent and the proportion of meso-lactide is 7 percent.
Example 9:
the reaction process of the polylactic acid with the depolymerization regularity of 99% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with 99% regularityMn=40 kg/mol, pdi=1.81, l-LA: 50%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 250 ℃, and distilling under reduced pressure at the pressure of 0.07 mbar to obtain the product lactide with the yield of 96% through weighing and verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the proportion of racemic lactide is 90%, and the proportion of meso-lactide is 10%.
Example 10:
the reaction process of the polylactic acid with the depolymerization regularity of 95% in this example is as follows:
the experimental process comprises the following steps:
taking a 25 mL round-bottom flask, adding 10 g polylactic acid with a degree of regularity of 95%Mn=40 kg/mol, pdi=1.81, l-LA: 50%) and then adding 95 mg ZnCl 2 And equimolar amount of 1, 10-phenanthroline, heating to 220 ℃, distilling under reduced pressure at a pressure of 0.07 mbar for reaction of 1.8 h, and weighing to obtain product lactide with a yield of 95% verified by high performance liquid chromatography and nuclear magnetic resonance spectroscopy, wherein the proportion of racemic lactide is 92%, and the proportion of meso-lactide8%.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.

Claims (6)

1. A method for depolymerizing high-regularity polylactic acid is characterized in that the high-regularity polylactic acid is catalyzed and depolymerized by a zinc complex catalyst at the temperature of 30-300 ℃ and under the condition of 0.001-100 mbar to obtain lactide, wherein the high-regularity polylactic acid is obtainedPm = 0.85～1.0；
The zinc complex catalyst is prepared by directly adding 1, 10-phenanthroline and a metallic zinc compound into a depolymerization reaction system in situ;
the metal zinc compound is zinc chloride or zinc acetate.
2. The method for depolymerizing highly-regular polylactic acid according to claim 1, wherein the zinc-based complex is added in an amount of 0.01 to 20% wt% of the highly-regular polylactic acid.
3. The method for depolymerizing highly regular polylactic acid according to claim 1, wherein the highly regular polylactic acid has a number average molecular weight of 10 2 ～10 7 g/mol。
4. The method for depolymerizing a high-regularity polylactic acid according to claim 1, wherein the content of L-configuration in the high-regularity polylactic acid is 1 to 100%.
5. The method for depolymerizing a high-regularity polylactic acid according to claim 1, wherein the polymerized units of the high-regularity polylactic acid have the following structure:
wherein x and y represent the content of L-form and D-form in the highly regular polylactic acid, respectively.
6. The method for depolymerizing polylactic acid with high regularity according to claim 1, wherein the proportion of meso-lactide in the obtained lactide is 2 to 10%.
CN202210890799.0A 2022-07-27 2022-07-27 Zinc complex catalyst and method for depolymerizing high-regularity polylactic acid and recycling racemic lactide Active CN115073418B (en)

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