CN111333825A - Preparation method of carbon dioxide-based polyester-polycarbonate quaternary block copolymer - Google Patents
Preparation method of carbon dioxide-based polyester-polycarbonate quaternary block copolymer Download PDFInfo
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- CN111333825A CN111333825A CN202010337337.7A CN202010337337A CN111333825A CN 111333825 A CN111333825 A CN 111333825A CN 202010337337 A CN202010337337 A CN 202010337337A CN 111333825 A CN111333825 A CN 111333825A
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 17
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 16
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 16
- 229920001400 block copolymer Polymers 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229920003046 tetrablock copolymer Polymers 0.000 claims description 5
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- LVRCYPYRKNAAMX-UHFFFAOYSA-M bis(triphenylphosphine)iminium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LVRCYPYRKNAAMX-UHFFFAOYSA-M 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 229920000359 diblock copolymer Polymers 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 polymethylethylene carbonate Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of high polymer material synthesis, and relates to a preparation method of a carbon dioxide-based biodegradable polyester-polycarbonate quaternary block copolymer, wherein the block copolymer comprises a diblock copolymer (A-B type); the segment A is prepared from propylene oxide, cyclohexene oxide and CO2The segment B is aromatic polyester obtained by ring-opening polymerization of propylene oxide, cyclohexene oxide and phthalic anhydride. The invention adopts commercial Lewis acid-base couple as catalyst, successfully introduces phthalic anhydride and cyclohexene oxide on the main chain of polymethyl ethylene carbonate (PPC) by one-pot one-step method, greatly improves the glass transition temperature, the thermal stability and the tensile strength of the PPC, eliminates the problem of metal catalyst residue in the prior art, enlarges the range of metal catalyst residue, and has the advantages of simple preparation process, low cost, high stability and high yieldThe application range of the PPC material.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a preparation method of a carbon dioxide-based polyester-polycarbonate quaternary block copolymer.
Background
With the rapid development of global industrialization, a large amount of fossil energy is developed and used, which not only causes the gradual depletion of traditional energy, but also leads to the increase of carbon dioxide emission and forms a serious greenhouse effect. Meanwhile, a large amount of non-degradable plastic products are produced, and the waste thereof causes serious 'white pollution'. CO promotion by both energy and environmental pressures2Research and application of base polymers.
First utilization of CO since 19692Synthesis of a polymethylethylene carbonate (PPC) material, synthesis and modification of the PPC material have been widely studied. But due to the glass transition temperature (T) of PPCg) Lower (<46 ℃ and not high in tensile strength (<40MPa) and the industrial application thereof is greatly limited, so that the material performance can be greatly improved by modifying the PPC in a way of blending with other materials or copolymerizing with other monomers, thereby expanding the application range thereof.
The rigid component is introduced into the PPC flexible chain segment by a copolymerization method, so that the T of the PPC flexible chain segment can be greatly improvedg. The research shows that the T of PPC is adjusted within the range of 50-100 ℃ by adding cyclohexene oxide for cohesive energygHowever, the introduction of a large amount of relatively expensive epoxycyclohexane is not favorable for cost control. If only phthalic anhydride is incorporated into the PPC segment, its TgCan only be controlled below 62 ℃. Therefore, the epoxy cyclohexane and the phthalic anhydride are simultaneously introduced into the PPC chain segment, so that the T of the material can be effectively regulated and controlledgThe production cost can be controlled at the temperature of more than 90 ℃.
Disclosure of Invention
The object of the invention is to overcome the disadvantages of the prior art by means of propylene oxide, cyclohexene oxide, phthalic anhydride and CO2The copolymerization of the block copolymer can effectively improve the glass transition temperature and the tensile strength of the PPC(ii) a The quaternary block copolymer prepared in large scale by adopting the organic boron/organic amine nonmetal catalyst has the characteristics of adjustable composition proportion, higher glass transition temperature, higher tensile property, good light transmittance, excellent foaming property and the like, and is a biodegradable material with considerable application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon dioxide-based polyester-polycarbonate tetrablock copolymer has the following structural formula:
wherein a is more than or equal to 1, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 1, and a, b, c and d are integers.
The preparation process comprises the following steps:
the preparation method of the carbon dioxide-based polyester-polycarbonate tetrablock copolymer comprises the following steps: adding a monomer, a catalyst and a solvent into a high-pressure reaction kettle, introducing carbon dioxide, placing the mixture into an oil bath kettle for ring-opening polymerization reaction, dissolving a product by using dichloromethane after the reaction is finished, adding a small amount of acid to terminate the reaction, and finally separating out the product in ethanol; the monomers are epoxide, phthalic anhydride and CO2Epoxides include propylene oxide and cyclohexane oxide.
Preferably, in the above-mentioned production method: the molar ratio of the epoxide to phthalic anhydride is greater than 1; the molar ratio of the propylene oxide to the (epoxycyclohexane + phthalic anhydride) is 2-10: 1; the CO is2The internal pressure range after the reaction kettle is filled is 0.1-4.0 MPa.
Preferably, in the above-mentioned production method: the catalyst is a Lewis acid-base pair composite catalyst; the Lewis acid is an organic boron compound; the lewis base is an organic amine (salt).
Preferably, in the above-mentioned production method: the organic boron compound is triethylboron, triphenylboron or tri (pentafluorophenyl) boron; the organic amine (salt) is bis (triphenyl phosphoranylidene) ammonium chloride, tetra-n-butylammonium bromide or 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
Preferably, in the above-mentioned production method: the feeding ratio of the catalyst to the epoxide is 1: 100-3000.
Preferably, in the above-mentioned production method: the reaction temperature of the ring-opening polymerization reaction is 40-100 ℃, and the reaction time is 4-72 h.
Compared with the prior art, the invention has the following technical effects: the invention adopts a commercialized non-metal catalyst to synthesize the polyester-polycarbonate block copolymer by a one-pot one-step method, and can effectively avoid the residue problem of the metal catalyst; the introduction of the rigid component can effectively improve the glass transition temperature and the tensile strength of the material; the material has good light transmission and foaming performance, and has considerable application prospect.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of the polymer prepared in example 1 of the present invention1H NMR chart;
FIG. 2 is a nuclear magnetic carbon spectrum of the polymer prepared in example 113C NMR chart.
Detailed Description
Example 1
Under the anhydrous and oxygen-free conditions, 30mmol phthalic anhydride, 30mmol cyclohexene oxide, 30mmol propylene oxide, 0.06mmol bis (triphenylphosphine) ammonium chloride, 0.12mmol triethyl boron and 15mL tetrahydrofuran are added into a 100mL high-pressure reaction kettle, 1MPa carbon dioxide is introduced, the reaction kettle is cooled to room temperature by cold water after 24 hours of reaction in a 70 ℃ oil bath kettle, and unreacted carbon dioxide is slowly released. Adding dichloromethane to dissolve the product, dripping a proper amount of 1M hydrochloric acid methanol solution to quench the reaction, separating out a polymer from ethanol, and measuring the molecular weight, the glass transition temperature, the polycarbonate content and the tensile strength after vacuum drying. Mn＝53.2kDa，PDI＝1.15，Tg95.9 deg.C, 44% polycarbonate content, high tensile strengthDegree is 53.3 MPa.
Example 2
Under the anhydrous and oxygen-free conditions, 15mmol of phthalic anhydride, 30mmol of cyclohexene oxide, 30mmol of propylene oxide, 0.06mmol of bis (triphenylphosphine) ammonium chloride, 0.12mmol of triethylboron and 15mL of tetrahydrofuran are added into a 100mL high-pressure reaction kettle, 1MPa of carbon dioxide is introduced, the mixture reacts in an oil bath kettle at 70 ℃ for 24 hours, then the reaction kettle is cooled to room temperature by cold water, and unreacted carbon dioxide is slowly released. Adding dichloromethane to dissolve the product, dripping a proper amount of 1M hydrochloric acid methanol solution to quench the reaction, separating out a polymer from ethanol, and measuring the molecular weight, the glass transition temperature, the polycarbonate content and the tensile strength after vacuum drying. Mn＝58.7kDa，PDI＝1.17，Tg94.7 ℃, polycarbonate content 70% and tensile strength 48.0 MPa.
Example 3
Under the anhydrous and oxygen-free conditions, 45mmol of phthalic anhydride, 30mmol of cyclohexene oxide, 30mmol of propylene oxide, 0.06mmol of bis (triphenylphosphine) ammonium chloride, 0.12mmol of triethylboron and 15mL of tetrahydrofuran are added into a 100mL high-pressure reaction kettle, 1MPa of carbon dioxide is introduced, the mixture reacts in an oil bath kettle at 70 ℃ for 24 hours, then the reaction kettle is cooled to room temperature by cold water, and unreacted carbon dioxide is slowly released. Adding dichloromethane to dissolve the product, dripping a proper amount of 1M hydrochloric acid methanol solution to quench the reaction, separating out a polymer from ethanol, and measuring the molecular weight, the glass transition temperature, the polycarbonate content and the tensile strength after vacuum drying. Mn＝52.1kDa，PDI＝1.16，Tg101.5 ℃, 11% polycarbonate content, 54.8MPa tensile strength.
From the above results, it can be seen that the polyester-polycarbonate tetrablock copolymer obtained by the present invention has adjustable glass transition temperature and higher tensile strength, and simultaneously has good light transmittance and foaming performance. The method is a method for effectively improving the PPC performance, and the product has a great application prospect.
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (7)
1. A carbon dioxide-based polyester-polycarbonate tetrablock copolymer has the following structural formula:
wherein a is more than or equal to 1, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 1, and a, b, c and d are integers.
2. The method for preparing the carbon dioxide-based polyester-polycarbonate tetrablock copolymer as defined in claim 1, which comprises the steps of: adding a monomer, a catalyst and a solvent into a high-pressure reaction kettle, introducing carbon dioxide, placing the mixture into an oil bath kettle for ring-opening polymerization reaction, dissolving a product by using dichloromethane after the reaction is finished, adding a small amount of acid to terminate the reaction, and finally separating out the product in ethanol; the monomers are epoxide, phthalic anhydride and CO2Epoxides include propylene oxide and cyclohexane oxide.
3. The method of claim 2, wherein: the molar ratio of the epoxide to phthalic anhydride is greater than 1; the molar ratio of the propylene oxide to the (epoxycyclohexane + phthalic anhydride) is 2-10: 1; the CO is2The internal pressure range after the reaction kettle is filled is 0.1-4.0 MPa.
4. The method of claim 2, wherein: the catalyst is a Lewis acid-base pair composite catalyst; the Lewis acid is an organic boron compound; the lewis base is an organic amine (salt).
5. The method of claim 4, wherein: the organic boron compound is triethylboron, triphenylboron or tri (pentafluorophenyl) boron; the organic amine (salt) is bis (triphenyl phosphoranylidene) ammonium chloride, tetra-n-butylammonium bromide or 1, 8-diazabicyclo [5.4.0] undec-7-ene.
6. The method of claim 2, wherein: the feeding ratio of the catalyst to the epoxide is 1: 100-3000.
7. The method of claim 2, wherein: the reaction temperature of the ring-opening polymerization reaction is 40-100 ℃, and the reaction time is 4-72 h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072691A (en) * | 2021-04-13 | 2021-07-06 | 上海华峰新材料研发科技有限公司 | Polycarbonate cyclohexene ester copolymer and preparation method thereof |
| CN113929890A (en) * | 2021-09-22 | 2022-01-14 | 中山大学 | Epichloropropane, phthalic anhydride, epoxypropane and carbon dioxide quaternary block copolymer and preparation method thereof |
| CN114524930A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Quaternary copolymer containing phthalic anhydride and ethylene oxide |
| CN114525025A (en) * | 2021-09-23 | 2022-05-24 | 山东联欣环保科技有限公司 | Copolymer foam material and preparation method and application thereof |
| CN114524929A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Preparation method of carbon dioxide-based quadripolymer |
| CN115044024A (en) * | 2022-06-08 | 2022-09-13 | 中山大学 | Biodegradable copolymer for plasticizing and toughening polyvinyl chloride and preparation method thereof |
| EP4059981A1 (en) * | 2021-03-17 | 2022-09-21 | King Abdullah University of Science and Technology | Ethylene oxide-based copolymers |
| CN115521591A (en) * | 2022-11-07 | 2022-12-27 | 山东联欣环保科技有限公司 | High-toughness composition of carbon dioxide-based quadripolymer and preparation method thereof |
| WO2023045889A1 (en) * | 2021-09-23 | 2023-03-30 | 山东联欣环保科技有限公司 | Degradable barrier composition, preparation method therefor and use thereof |
| WO2023066269A1 (en) * | 2021-10-19 | 2023-04-27 | 山东联欣环保科技有限公司 | Method for mixed feeding of phthalic anhydride and propylene oxide, equipment, and application |
| CN116355194A (en) * | 2023-05-25 | 2023-06-30 | 山东联欣环保科技有限公司 | Method for improving barrier property of polycarbonate |
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Cited By (21)
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| EP4059981A1 (en) * | 2021-03-17 | 2022-09-21 | King Abdullah University of Science and Technology | Ethylene oxide-based copolymers |
| CN115109241A (en) * | 2021-03-17 | 2022-09-27 | 阿卜杜拉国王科技大学 | Ethylene oxide based copolymers |
| CN113072691B (en) * | 2021-04-13 | 2023-08-01 | 上海华峰新材料研发科技有限公司 | Polycyclohexene carbonate copolymer and preparation method thereof |
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Application publication date: 20200626 Assignee: Hebei Zhongmei Xuyang Energy Co.,Ltd. Assignor: SUN YAT-SEN University Contract record no.: X2022440000020 Denomination of invention: A preparation method of carbon dioxide based polyester polycarbonate quaternary block copolymer License type: Common License Record date: 20220328 |
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