CN117683040A - A depolymerization method of bio-based glass-like polycarbonate - Google Patents
A depolymerization method of bio-based glass-like polycarbonate Download PDFInfo
- Publication number
- CN117683040A CN117683040A CN202311636709.6A CN202311636709A CN117683040A CN 117683040 A CN117683040 A CN 117683040A CN 202311636709 A CN202311636709 A CN 202311636709A CN 117683040 A CN117683040 A CN 117683040A
- Authority
- CN
- China
- Prior art keywords
- depolymerization
- polycarbonate
- bio
- mixture
- based glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a depolymerization method of bio-based glass-imitation polycarbonate, which is characterized by comprising the following steps: (a) Adding the bio-based glass-like polycarbonate to an organic solvent to obtain a mixture; (b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride; (c) Separating the depolymerized solution to obtain a low-molecular chemical; the invention can better promote the depolymerization of the bio-based glass-like polycarbonate by limiting the types and the dosage of the organic solvent and the depolymerization reagent, improves the depolymerization efficiency and shortens the time, and the purpose of recycling the waste bio-based glass-like polycarbonate is achieved by collecting and utilizing the low-molecular chemicals obtained by the reaction.
Description
Technical Field
The invention relates to the technical field of polycarbonate depolymerization, in particular to a depolymerization method of bio-based glass-imitated polycarbonate.
Background
Bio-based polycarbonates are prepared by substituting isosorbide as a comonomer for bisphenol a. Because the raw materials for preparing the bio-based polycarbonate have no bisphenol A, the influence of bisphenol A on human endocrine and the harm to the environment are avoided, and therefore, the bio-based polycarbonate has better application prospect than bisphenol A polycarbonate.
With the wide use of bio-based polycarbonates, the treatment of waste bio-based polycarbonates is becoming more and more important, however, there is no economical benefit and a treatment method of bio-based polycarbonates with higher treatment efficiency.
In view of this, the present invention has been made.
Disclosure of Invention
Object of the inventionThe depolymerization method has high depolymerization efficiency, can depolymerize the bio-based glass-like polycarbonate fully, and can collect and utilize separated low-molecular chemicals to recycle the waste bio-based glass-like polycarbonate.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the first aspect of the invention provides a depolymerization method of a bio-based glass-like polycarbonate, the depolymerization method comprising the steps of:
(a) Adding the bio-based glass-like polycarbonate to an organic solvent to obtain a mixture;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride;
(c) And separating the depolymerized solution to obtain the low-molecular chemical.
Preferably, the organic solvent is a mixed solution of methanol, toluene and xylene.
Preferably, the volume ratio of the methanol to the toluene to the dimethylbenzene is 10:2-4:1-2. By limiting the types and the amounts of the organic solvents, the depolymerization of the bio-based glass-like polycarbonate can be better promoted, and the depolymerization efficiency can be improved.
Preferably, the concentration of biobased glass-like polycarbonate in the mixture is 0.05 to 0.2g/ml.
Preferably, the final concentration of the depolymerization reagent to be added is 0.05 to 0.1g/ml.
Preferably, the mol ratio of the ethanolamine to the potassium hydroxide to the zinc chloride is (4-6) to (7-9) to (1-3).
Preferably, the mol ratio of the ethanolamine, the potassium hydroxide and the zinc chloride is 5:8:2.
The invention can depolymerize bio-based polycarbonate better under the combined action of the reagents by limiting the depolymerization reagent specifically, has high depolymerization efficiency in short time and more thorough depolymerization.
Preferably, the depolymerization reaction temperature is 60-90 ℃ and the reaction time is 30-40 min.
Preferably, the bio-based glass-like polycarbonate is 1, 4-cyclohexanedimethanol-based bio-polycarbonate, and the structural formula is as follows:
the bio-based glass-like polycarbonate copolymer is prepared by melt polycondensation reaction of bio-based isosorbide, 1, 4-cyclohexane-dimethanol and diphenyl carbonate by using tetraethylammonium hydroxide as a catalyst.
Preferably, the low molecular chemicals include isosorbide and 1, 4-cyclohexanedimethanol.
Compared with the prior art, the invention has the beneficial effects that at least:
the invention can better promote the depolymerization of the bio-based glass-imitation polycarbonate by limiting the types and the dosage of the organic solvent and the depolymerization reagent, improves the depolymerization efficiency, shortens the time for use, and achieves the aim of recycling the waste bio-based glass-imitation polycarbonate by utilizing the low-molecular chemicals obtained by the reaction.
Detailed Description
The technical scheme of the present invention will be described in detail with reference to examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and thus are merely examples, and are not intended to limit the scope of the present invention.
It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
The embodiment of the invention provides a depolymerization method of bio-based glass-like polycarbonate, which comprises the following steps:
(a) Adding the bio-based glass-like polycarbonate to an organic solvent to obtain a mixture;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride;
(c) And separating the depolymerized solution to obtain the low-molecular chemical.
In one embodiment, the organic solvent is a mixture of methanol, toluene and xylene.
Further, the volume ratio of the methanol to the toluene to the dimethylbenzene is 10:2-4:1-2.
The method can better promote the depolymerization of the bio-based glass-like polycarbonate by limiting the types and the amounts of the organic solvent and the depolymerization reagent, improves the depolymerization efficiency, shortens the time for use, and achieves the aim of recycling the waste bio-based glass-like polycarbonate by utilizing the low-molecular chemicals obtained by the reaction.
In another embodiment, the concentration of biobased glass-like polycarbonate in the mixture is 0.05 to 0.2g/ml, and may specifically be 0.05g/ml, 0.1g/ml, 0.15g/ml, or 0.2g/ml.
To better promote depolymerization of the bio-based glass-imitation polycarbonate, in some embodiments, the depolymerization reagent is added at a final concentration of 0.05 to 0.1g/ml, which may specifically be 0.05g/ml or 0.1g/ml.
In yet another embodiment, the molar ratio of ethanolamine, potassium hydroxide, and zinc chloride is (4-6): (7-9): (1-3).
Preferably, the mol ratio of the ethanolamine, the potassium hydroxide and the zinc chloride is 5:8:2.
The invention can depolymerize bio-based polycarbonate better under the combined action of the reagents by limiting the depolymerization reagent specifically, and has short time, high depolymerization efficiency and more thorough depolymerization.
The depolymerization reaction parameters are not strictly limited in the present invention, and may be selected according to the depolymerization efficiency, and preferably, in some embodiments, the depolymerization reaction temperature is 60 to 90 ℃ and the reaction time is 30 to 40min.
In one embodiment, the biobased glass-imitation polycarbonate is a 1, 4-cyclohexanedimethanol-based biopolycarbonate having the structural formula:
in another embodiment, -the low molecular chemicals obtained after depolymerization of the above-mentioned 1, 4-cyclohexanedimethanol based bio-polycarbonates comprise isosorbide and 1, 4-cyclohexanedimethanol.
The technical scheme of the invention is further described in detail through the following specific embodiments.
Example 1
This example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 10:2:1; the concentration of bio-based polycarbonate in the mixture was 0.05g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride in a molar ratio of 6:7:3; the final concentration of the depolymerization reagent added is 0.05g/ml; the depolymerization reaction temperature is 60 ℃ and the reaction time is 40min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Example 2
This example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 5:2:1; the concentration of bio-based polycarbonate in the mixture was 0.2g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride in a molar ratio of 4:9:1; the final concentration of the depolymerization reagent added is 0.1g/ml; the depolymerization reaction temperature is 90 ℃ and the reaction time is 30min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Example 3
This example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 10:3:2; the concentration of bio-based polycarbonate in the mixture was 0.1g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride in a molar ratio of 5:8:2; the final concentration of the depolymerization reagent added is 0.15g/ml; the depolymerization reaction temperature is 80 ℃ and the reaction time is 35min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Comparative example 1
This comparative example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 10:3:2; the concentration of bio-based polycarbonate in the mixture was 0.1g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride in a molar ratio of 2:11:2; the final concentration of the depolymerization reagent added is 0.15g/ml; the depolymerization reaction temperature is 80 ℃ and the reaction time is 35min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Comparative example 2
This comparative example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 10:3:2; the concentration of bio-based polycarbonate in the mixture was 0.1g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine and potassium hydroxide in a molar ratio of 5:8; the final concentration of the depolymerization reagent added is 0.15g/ml; the depolymerization reaction temperature is 80 ℃ and the reaction time is 35min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Comparative example 3
This comparative example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol, toluene and xylene in a volume ratio of 10:3:2; the concentration of bio-based polycarbonate in the mixture was 0.1g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of potassium hydroxide and zinc chloride in a molar ratio of 8:2; the final concentration of the depolymerization reagent added is 0.15g/ml; the depolymerization reaction temperature is 80 ℃ and the reaction time is 35min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Comparative example 4
This comparative example is a method for depolymerizing 1, 4-cyclohexanedimethanol-based bio-polycarbonate, comprising the steps of:
(a) Adding polycarbonate into an organic solvent to obtain a mixture, wherein the organic solvent is a mixed solution of methanol and toluene in a volume ratio of 10:3; the concentration of bio-based polycarbonate in the mixture was 0.1g/ml;
(b) Adding a depolymerization reagent into the mixture to carry out depolymerization reaction, wherein the depolymerization reagent consists of ethanolamine, potassium hydroxide and zinc chloride in a molar ratio of 5:8:2; the final concentration of the depolymerization reagent added is 0.15g/ml; the depolymerization reaction temperature is 80 ℃ and the reaction time is 35min;
(c) And separating the depolymerized solution to obtain the isosorbide and the 1, 4-cyclohexanedimethanol.
Experimental example
Depolymerization experiments were performed on 1, 4-cyclohexanedimethanol-based bio-polycarbonates according to the depolymerization methods of examples 1 to 3 and comparative examples 1 to 4, respectively, and the conversion of the bio-based glass-like polycarbonates was measured and calculated, and the calculation results are shown in table 1:
TABLE 1
| Group of | Conversion rate |
| Example 1 | 91.6％ |
| Example 2 | 87.9％ |
| Example 3 | 97.2％ |
| Comparative example 1 | 76.3％ |
| Comparative example 2 | 72.1％ |
| Comparative example 3 | 63.8％ |
| Comparative example 4 | 82.7％ |
As can be seen from table 1:
the depolymerization methods of the embodiment and the comparative example can realize depolymerization of the bio-based glass-like polycarbonate, and compared with the comparative example, the depolymerization method of the embodiment of the application has higher depolymerization efficiency and can better promote degradation of the bio-based glass-like polycarbonate in a shorter time.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311636709.6A CN117683040A (en) | 2023-12-01 | 2023-12-01 | A depolymerization method of bio-based glass-like polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311636709.6A CN117683040A (en) | 2023-12-01 | 2023-12-01 | A depolymerization method of bio-based glass-like polycarbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117683040A true CN117683040A (en) | 2024-03-12 |
Family
ID=90129378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311636709.6A Pending CN117683040A (en) | 2023-12-01 | 2023-12-01 | A depolymerization method of bio-based glass-like polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117683040A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005325219A (en) * | 2004-05-14 | 2005-11-24 | Nippon Carbide Ind Co Inc | Polycarbonate diol and process for producing the same |
| US20130261198A1 (en) * | 2012-03-30 | 2013-10-03 | Husnu Alp Alidedeoglu | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| CN113480411A (en) * | 2021-06-18 | 2021-10-08 | 北京市农林科学院 | Depolymerization method of polycarbonate micro plastic and electrochemical detection method thereof |
| CN113912476A (en) * | 2021-09-27 | 2022-01-11 | 中国科学院青岛生物能源与过程研究所 | Method for depolymerizing polycarbonate material by using amine alcohol system |
| CN115244120A (en) * | 2020-01-23 | 2022-10-25 | 普莱米尔塑料公司 | Method and system for depolymerizing waste plastics |
-
2023
- 2023-12-01 CN CN202311636709.6A patent/CN117683040A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005325219A (en) * | 2004-05-14 | 2005-11-24 | Nippon Carbide Ind Co Inc | Polycarbonate diol and process for producing the same |
| US20130261198A1 (en) * | 2012-03-30 | 2013-10-03 | Husnu Alp Alidedeoglu | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| CN115244120A (en) * | 2020-01-23 | 2022-10-25 | 普莱米尔塑料公司 | Method and system for depolymerizing waste plastics |
| CN113480411A (en) * | 2021-06-18 | 2021-10-08 | 北京市农林科学院 | Depolymerization method of polycarbonate micro plastic and electrochemical detection method thereof |
| CN113912476A (en) * | 2021-09-27 | 2022-01-11 | 中国科学院青岛生物能源与过程研究所 | Method for depolymerizing polycarbonate material by using amine alcohol system |
Non-Patent Citations (1)
| Title |
|---|
| 刘红阳: "废旧PET/PC塑料回收与化学再生利用现状", 《橡塑资源利用》, no. 06, 31 December 2005 (2005-12-31), pages 23 - 27 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106170334B (en) | Nanofiltration membranes and methods of use | |
| Liu et al. | Chemical recycling to monomers: Industrial Bisphenol‐A‐Polycarbonates to novel aliphatic polycarbonate materials | |
| Dang et al. | An approach to chemical recycling of epoxy resin cured with amine using nitric acid | |
| JP5781939B2 (en) | Adjustable polymer composition | |
| CN112876652A (en) | Rosin-based epoxy glass polymer material and preparation method thereof | |
| EP4225719A1 (en) | Styrene-assisted depolymerization of polyolefins | |
| Olazabal et al. | Upcycling of BPA-PC into trimethylene carbonate by solvent assisted organocatalysed depolymerisation | |
| CN114409880A (en) | Preparation method of recyclable bio-based polyester | |
| CN117683040A (en) | A depolymerization method of bio-based glass-like polycarbonate | |
| JP3422647B2 (en) | Method for obtaining dialkyl carbonate and bisphenol from polycarbonate | |
| CN102863369A (en) | Method for preparing 1, 1-bis (tert-butyl peroxo) cyclohexane | |
| CN111116359A (en) | High-performance polyester alcoholysis solution and waste polyester alcoholysis method | |
| Tong et al. | New strategies for synthesis of amino‐functionalized poly (propylene carbonate) over SalenCo (III) Cl catalyst | |
| CN117801254A (en) | A method for recovering and reusing amine catalyst in PC reaction solution | |
| CN118851884A (en) | A method for directional chemical depolymerization of bisphenol A type polycarbonate plastic | |
| KR20160121871A (en) | Method for preparing polyalkylenecarbonate | |
| CN116082629A (en) | Method for synthesizing poly(arylene ether nitrile) under the condition of no water agent | |
| CN111019110B (en) | Tail gas treatment method for combined hydrofluoric acid and organic carbonate | |
| CN119684577B (en) | A bio-based closed-loop recyclable thermoplastic elastomer and its preparation method | |
| CN117777424B (en) | Synthesis method of carbon dioxide-based aromatic ring-aliphatic chain composite polycarbonate product | |
| CN117024255B (en) | A method for catalytic degradation of polycarbonate using a phosphazene base system | |
| CN121181868B (en) | A liquid recycled polyester diol based on waste PET and its preparation method | |
| CN115785426B (en) | Polycarbonate and preparation method thereof | |
| Morinaga et al. | Acid‐Promoted Depolymerization of Poly (hydroxyurethane) s to Five‐Membered Cyclic Carbonates Toward Chemical Recycling | |
| JP3866876B2 (en) | Method for recovering dimethyl terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |