CN116535625A - Carbon dioxide-based polyester-polycarbonate biodegradable copolymer and preparation method thereof - Google Patents
Carbon dioxide-based polyester-polycarbonate biodegradable copolymer and preparation method thereof Download PDFInfo
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- CN116535625A CN116535625A CN202310509265.3A CN202310509265A CN116535625A CN 116535625 A CN116535625 A CN 116535625A CN 202310509265 A CN202310509265 A CN 202310509265A CN 116535625 A CN116535625 A CN 116535625A
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- carbon dioxide
- polycarbonate
- polylactic acid
- based polyester
- biodegradable copolymer
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 77
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 77
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 54
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 54
- 229920001577 copolymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004626 polylactic acid Substances 0.000 claims abstract description 49
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 22
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000012456 homogeneous solution Substances 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000002879 Lewis base Substances 0.000 claims description 11
- 150000007527 lewis bases Chemical class 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005580 one pot reaction Methods 0.000 claims description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 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 claims description 7
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 2
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 2
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims description 2
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920006238 degradable plastic Polymers 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- -1 Chen Xuesai Chemical compound 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- 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
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- 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 discloses a carbon dioxide-based polyester-polycarbonate biodegradable copolymer and a preparation method thereof, wherein the copolymer is obtained by copolymerizing propylene oxide, phthalic anhydride, carbon dioxide and polylactic acid, and can also utilize carbon dioxide (CO) 2 ) The prepared polyester-polycarbonate (PPC-P) is obtained by copolymerization with polylactic acid (PLA), the preparation method has simple process, abundant and easily obtained raw materials, and the preparation process is stable and reliable. By copolymerization of PLA and PPC-P, not only can a crystallization structure be introduced into the structure of PPC-P to change the structure into a semi-crystalline copolymer, but also the heat distortion temperature of PPC-P can be improved, and the toughness of PPC-P can be improved within a certain raw material molar ratio range. The prepared PPC-P-co-PLA copolymer has the advantages of high transparency, good degradability, controllable molecular weight and the like on the basis of keeping the original excellent properties of PPC-P and PLA. The invention not only prepares CO 2 The base degradable plastic has simple and feasible preparation process thought and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a carbon dioxide-based polyester-polycarbonate biodegradable copolymer and a preparation method thereof.
Background
Control of carbon emissions, reduction of carbon dioxide (CO) 2 ) Is one of the important ways of green low-carbon and cyclic development, and utilizes carbon dioxide (CO 2 ) The ring-opening polymerization reaction with propylene oxide can realize carbon neutralization, energy conservation and emission reduction, and can prepare the polycarbonate (PPC) which is degradable, high in light transmittance and wide in application range. In 2020, meng Yue, the PPC was modified with phthalic anhydride (CN 111378101A, J.CO 2 Util.2021,49,101558) to prepare polyester-polycarbonate (PPC-P) with more excellent performance, and then continuously modifying and optimizing the PPC-P, introducing a branching structure structurally by using a branching agent (CN 113896872A) in 2021 to reduce the melt index, and synthesizing carbon dioxide-based polyester-polycarbonate (CN 114736360A) containing double bonds in 2022, thus having great significance for the research of degradable plastics.
Polylactic acid (PLA) is linear aliphatic polyester, and degradation products are carbon dioxide and water, so that the polylactic acid has good biodegradability and environmental friendliness. PLA has good crystallinity, is a brittle material, and aims at the problems of insufficient toughness and poor durability of PLA, and the improvement of PLA performance by blending (physical modification) and copolymerization (chemical modification) is a research direction with higher feasibility at present. The main method for preparing the polylactic acid copolymer is ring-opening copolymerization of lactide, such as ring-opening copolymerization of alkylene oxide, phthalic anhydride and lactide into M n PLA-b-PPE-b-PLA block copolymer (Angew.chem.int.ed.2018, 57, 16893-16897) or M at 14.2kg/mol n A at 17.1kg/mol z C y (AB) x C y A z Pentablock terpolymers (polym.chem., 2020,11,1691-1695).
At present, carbon dioxide-based polycarbonate-polylactic acid copolymer is mainly prepared by CO 2 Obtained by ring-opening copolymerization of alkylene oxide and lactide, e.g. Chen Xuesai, etc. by CO 2 Synthesis of M by Ring-opening copolymerization of alkylene oxide and lactide n The catalyst was a Salen Cr (III) complex (Chinese J. Polym. Sci.2022,40, 1028-1033) with a PPC-PLA content of 14.5 kg/mol. However, the lactide ring-opening copolymerization is utilized, the preparation process is relatively complex, and the prepared copolymer has low molecular weight and is not suitable for large-scale production and application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a carbon dioxide-based polyester-polycarbonate biodegradable copolymer and a preparation method thereof, and the polymer prepared by the invention has adjustable molecular weight, biodegradability and good transparency; the preparation method of the copolymer has simple process, abundant and easily obtained raw materials and stable and reliable preparation process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a carbon dioxide-based polyester-polycarbonate biodegradable copolymer comprises degradable polyester-polycarbonate and polylactic acid, has semi-crystalline characteristics, and has a sequence structure comprising random blocks and the like, wherein the structure is shown as a formula (1); wherein a is more than or equal to 5 and less than or equal to 971, b is more than or equal to 10 and less than or equal to 2941,2, c is more than or equal to 3448,3 and d is more than or equal to 1388, and a, b, c and d are integers;
the preparation method adopts a one-pot one-step method and a one-pot two-step method, and the one-step method is characterized in that the polylactic acid homogeneous solution and other reagents are added into a high-pressure reaction kettle, carbon dioxide gas is introduced after the high-pressure reaction kettle is sealed, and the high-pressure reaction kettle is not opened any more in the reaction process. The two-stage process is characterized by a first reaction to form a polyester-polycarbonate (PPC-P), which is the first stage; then adding the polylactic acid homogeneous solution, which is the second step, and opening the high-pressure reaction kettle once only when the polylactic acid solution is added.
The preparation method of the carbon dioxide-based polyester-polycarbonate biodegradable copolymer adopts a one-pot one-step method, and comprises the following steps:
(1) Under the nitrogen atmosphere, dissolving polylactic acid in an organic solvent, and heating and stirring to form a polylactic acid homogeneous solution;
(2) Then adding the homogeneous solution of propylene oxide, phthalic anhydride, lewis base catalyst, organoborane and polylactic acid into a high-pressure reaction kettle under the nitrogen atmosphere, sealing the high-pressure reaction kettle, introducing carbon dioxide gas, heating and stirring to carry out copolymerization reaction;
(3) After the reaction is finished, the high-pressure reaction kettle is cooled to room temperature and then depressurized, and the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is obtained through dissolution, precipitation and drying.
Preferably, in the above method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the pressure of the carbon dioxide gas is 0.2-5MPa, the reaction temperature is 40-90 ℃, and the reaction time is 1-24 hours.
The preparation method of the carbon dioxide-based polyester-polycarbonate biodegradable copolymer adopts a one-pot two-step method and comprises the following steps:
(1) Under the nitrogen atmosphere, dissolving polylactic acid in an organic solvent, and heating and stirring to form a polylactic acid homogeneous solution;
(2) Under the nitrogen atmosphere, adding propylene oxide, phthalic anhydride, a Lewis base catalyst and organoborane into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing carbon dioxide gas, heating and stirring to carry out ring-opening copolymerization reaction to prepare polyester-polycarbonate (PPC-P);
(3) After the temperature of the high-pressure reaction kettle is reduced to room temperature and pressure is relieved, adding a polylactic acid homogeneous solution into the high-pressure reaction kettle to carry out copolymerization reaction of polyester-polycarbonate and polylactic acid in a nitrogen atmosphere;
(4) After the reaction is finished, the high-pressure reaction kettle is depressurized after being cooled to room temperature, and the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is obtained through dissolution, precipitation and drying.
Preferably, in the above method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the pressure of the carbon dioxide gas in the step (2) is 0.2-5MPa, the reaction temperature is 40-70 ℃, and the reaction time is 1-12 hours.
Preferably, in the preparation method of the carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the mass fraction of phthalic anhydride in the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is 10% -40%, the mass fraction of polycarbonate in the polymer is 10% -60%, the mass fraction of polyether in the polymer is less than 40%, and the mass fraction of polylactic acid in the polymer is 5% -40%.
Preferably, in the above method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the molar ratio of the lewis base catalyst to the organoborane is 1:0.5-8, the molar feed ratio of Lewis base catalyst to phthalic anhydride is 1:50-5000, the molar feed ratio of phthalic anhydride to propylene oxide is 1:2-100, wherein the molar feed ratio of polylactic acid to phthalic anhydride is 1:2-200.
Preferably, in the above-mentioned method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the lewis base is tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, triethyl methyl ammonium chloride, bis (triphenylphosphine) ammonium chloride, benzyl trimethyl ammonium chloride, or benzyl triethyl ammonium chloride; the organoborane is triethylboron, tripropylboron, tributylboron, tribenzylboron, trimethylamineboronic or dimethylamine boron.
Preferably, in the above method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the organic solvent is ethylene oxide or tetrahydrofuran.
Preferably, in the above-mentioned method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer, the polylactic acid has a weight average molecular weight of 20,000 to 500,000g/mol, including PLLA or PDLA.
Preferably, in the above preparation method, the number average molecular weight of the obtained carbon dioxide-based polyester-polycarbonate biodegradable copolymer is 10,000-500,000g/mol, the crystallinity is 0.2% -50%, the melting point is 150-200 ℃ and the heat distortion temperature is 50-70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention creatively copolymerizes the carbon dioxide-based polyester-polycarbonate and the polylactic acid, improves the crystallinity of the polyester-polycarbonate, and the addition of the polylactic acid has no adverse effect on the reaction of the original polyester-polycarbonate. By copolymerization of PLA and PPC-P, not only can a crystallization structure be introduced into the structure of PPC-P to change the structure into a semi-crystalline copolymer, but also the heat distortion temperature of PPC-P can be improved, and the toughness of PPC-P can be improved within a certain raw material molar ratio range.
(2) The experimental method of the invention is very simple and easy to implement, and can realize the preparation of the carbon dioxide-based polyester-polycarbonate biodegradable copolymer by a one-pot one-step method or a one-pot two-step method.
(3) The catalyst used in the invention is organoborane and Lewis base, is a nonmetallic catalyst, is safe and nontoxic, and has a huge application prospect in industrial synthesis because only one catalyst is needed. (4) Compared with PPC-P, the carbon dioxide-based polyester-polycarbonate biodegradable copolymer prepared by the invention has crystallization capability, improved heat distortion temperature, and unaffected light transmittance and degradability.
(5) The PPC-P-co-PLA copolymer prepared by the invention has the advantages of high transparency, good degradability, controllable molecular weight, high elongation at break and the like on the basis of keeping the original excellent properties of PPC-P and PLA. The invention not only prepares CO 2 The base degradable plastic has simple and feasible preparation process thought and is easy for industrial production.
Drawings
The drawings are to further illustrate and explain the present invention and are not to be construed as limiting the invention, and are intended to illustrate and explain the present invention by way of example only, and in the appended drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a carbon dioxide-based polyester-polycarbonate biodegradable copolymer obtained in example 2 of the present invention.
FIG. 2 is a GPC chart of a carbon dioxide-based polyester-polycarbonate biodegradable copolymer obtained in example 2 of the present invention.
FIG. 3 is a DSC of the carbon dioxide-based polyester-polycarbonate biodegradable copolymer obtained in example 2 of the present invention, wherein FIG. 3 (A) is a curve of 10℃per minute of primary temperature rise, FIG. 3 (B) is a curve of 10℃per minute of temperature decrease, and FIG. 3 (B) is a curve of 10℃per minute of secondary temperature rise.
Detailed Description
Example 1:
1.0g of polylactic acid is heated, stirred and dissolved in 8mL of propylene oxide to form transparent homogeneous solution in nitrogen atmosphere, then 4.0g of phthalic anhydride, 18.9g of propylene oxide, 63mg of bis (triphenylphosphine) ammonium chloride, 216 mu L of triethylboron solution and polylactic acid solution are sequentially added into a high-pressure reaction kettle, the high-pressure reaction kettle is sealed, 1.0MPa of carbon dioxide is filled, the reaction is carried out at 65 ℃ for 6 hours, the carbon dioxide pressure is released after the reaction is finished, dichloromethane is used for dissolving the product, the reaction is quenched by dilute hydrochloric acid/ethanol solution, the polymer is obtained by precipitation in ethanol, and the polymer is subjected to molecular weight test, nuclear magnetism analysis and thermal performance analysis after vacuum drying. Obtaining a polymerM n ＝55.8kg/mol,M w
＝85.2kg/mol,PDI＝1.52，T g ＝43.3℃，T m =163.2 ℃, heat distortion temperature 50 ℃, elongation at break 500%.
Example 2:
dissolving 1.0g of polylactic acid in 15.0g of ethylene oxide in a nitrogen atmosphere to form a transparent homogeneous solution, sequentially adding 4.0g of phthalic anhydride, 63mg of bis (triphenylphosphine) ammonium chloride, 216 mu L of triethylboron solution and polylactic acid/ethylene oxide solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, filling 1.0MPa of carbon dioxide, reacting for 6 hours at 65 ℃, releasing the pressure of the carbon dioxide after the reaction, dissolving a product by using dichloromethane, quenching the reaction by using a dilute hydrochloric acid/ethanol solution, precipitating in ethanol to obtain a polymer,the polymer was vacuum dried and then subjected to molecular weight testing, nuclear magnetic analysis and thermal performance analysis. Obtaining a polymerM n ＝54.1kg/mol,M w ＝77.5g/mol,PDI＝1.43，T g ＝36.7℃，T m =156.6 ℃, heat distortion temperature 52 ℃, elongation at break 38%.
Example 3:
in a nitrogen atmosphere, 12.6g of ethylene oxide, 4.0g of phthalic anhydride, 63mg of bis (triphenylphosphine) ammonium chloride and 216 mu L of triethylboron solution are sequentially added into a high-pressure reaction kettle, the high-pressure reaction kettle is sealed, 1.0MPa of carbon dioxide is filled, the reaction is carried out for 4 hours at 65 ℃, and the carbon dioxide pressure is released after the reaction kettle is cooled to room temperature. 1.0g of polylactic acid is heated, stirred and dissolved in 8ml of epoxypropane to form homogeneous solution, cooled to room temperature, added into a high-pressure reaction kettle, filled with 1.0MPa of carbon dioxide, reacted for 4 hours at 60 ℃, released from the pressure of the carbon dioxide after the reaction is finished, dissolved by methylene dichloride, quenched by dilute hydrochloric acid/ethanol solution, precipitated in ethanol to obtain polymer, and subjected to molecular weight test, nuclear magnetism analysis and thermal performance analysis after the polymer is dried in vacuum. Obtaining a polymerM n ＝64.8kg/mol,M w ＝78.5kg/mol,PDI＝1.21，T g ＝42.1℃，T m =163.6 ℃, heat distortion temperature 51 ℃, tensile strength 25.6MPa, elongation at break 7%.
Example 4:
in a nitrogen atmosphere, 12.6g of ethylene oxide, 4.0g of phthalic anhydride, 63mg of bis (triphenylphosphine) ammonium chloride and 216 mu L of triethylboron solution are sequentially added into a high-pressure reaction kettle, the high-pressure reaction kettle is sealed and filled with 1.0MPa of carbon dioxide for reaction for 4 hours at 65 ℃, the carbon dioxide pressure is released after cooling to room temperature, 1.0g of polylactic acid is heated and stirred to be dissolved in 7g of ethylene oxide to form a homogeneous solution, the homogeneous solution is cooled to room temperature and then added into the high-pressure reaction kettle, 1.0MPa of carbon dioxide is filled for reaction for 2 hours at 65 ℃, and after the reaction is finishedReleasing the pressure of carbon dioxide, dissolving the product by using dichloromethane, quenching the reaction by using dilute hydrochloric acid/ethanol solution, precipitating the solution in ethanol to obtain a polymer, and carrying out molecular weight test, nuclear magnetism analysis and thermal performance analysis on the polymer after vacuum drying. Obtaining a polymerM n ＝66.4kg/mol,M w ＝122.3kg/mol,PDI＝1.84，T g ＝36.1℃，T m =160.9 ℃, heat distortion temperature 50 ℃, tensile strength 19.4MPa, elongation at break 6%.
Comparative example 1: preparation of PPC-P Material
In a glove box, 12.6g of ethylene oxide, 4.0g of phthalic anhydride, 63mg of bis (triphenylphosphine) ammonium chloride and 216 mu L of triethylboron solution are sequentially added into a high-pressure reaction kettle, the high-pressure reaction kettle is sealed, 1.0MPa of carbon dioxide is filled, the reaction is carried out for 4 hours at 65 ℃, the carbon dioxide pressure is released after cooling to room temperature, a dichloromethane dissolution product is used, the reaction is quenched by a dilute hydrochloric acid/ethanol solution, a polymer is obtained by precipitation in ethanol, and the polymer is subjected to molecular weight test, nuclear magnetism analysis and thermal performance analysis after vacuum drying. M is M n ＝65.7kg/mol,M w ＝108.8kg/mol,PDI＝1.66，T g =39.9 ℃, no melting crystallization peak, a tensile strength of 37.2MPa, an elongation at break of 5%, a heat distortion temperature of 40 ℃.
Therefore, compared with the PPC-P material of comparative example 1, the carbon dioxide-based polyester-polycarbonate biodegradable copolymer prepared by the invention contains a melting crystallization peak, and the heat distortion temperature is obviously improved. The invention can be applied to the modification of PPC materials and PLA materials.
Claims (10)
1. A carbon dioxide-based polyester-polycarbonate biodegradable copolymer is characterized by comprising degradable polyester-polycarbonate and polylactic acid, and the structure of the copolymer is shown as a formula (1); wherein a is more than or equal to 5 and less than or equal to 971, b is more than or equal to 10 and less than or equal to 2941,2, c is more than or equal to 3448,3 and d is more than or equal to 1388, and a, b, c and d are integers;
2. the method for preparing the carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 1, which is characterized by adopting a one-pot one-step method comprising the steps of:
(1) Under the nitrogen atmosphere, dissolving polylactic acid in an organic solvent, and heating and stirring to form a polylactic acid homogeneous solution;
(2) Then adding the homogeneous solution of propylene oxide, phthalic anhydride, lewis base catalyst, organoborane and polylactic acid into a high-pressure reaction kettle under the nitrogen atmosphere, sealing the high-pressure reaction kettle, introducing carbon dioxide gas, heating and stirring to carry out copolymerization reaction;
(3) After the reaction is finished, the high-pressure reaction kettle is cooled to room temperature and then depressurized, and the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is obtained through dissolution, precipitation and drying.
3. The method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2, wherein the pressure of the carbon dioxide gas is 0.2 to 5MPa, the reaction temperature is 40 to 90 ℃ and the reaction time is 1 to 24 hours.
4. The method for preparing the carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 1, which is characterized by adopting a one-pot two-step method comprising the following steps:
(1) Under the nitrogen atmosphere, dissolving polylactic acid in an organic solvent, and heating and stirring to form a polylactic acid homogeneous solution;
(2) Under the nitrogen atmosphere, adding propylene oxide, phthalic anhydride, a Lewis base catalyst and organoborane into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing carbon dioxide gas, heating and stirring to carry out ring-opening copolymerization reaction to prepare polyester-polycarbonate (PPC-P);
(3) After the temperature of the high-pressure reaction kettle is reduced to room temperature and pressure is relieved, adding a polylactic acid homogeneous solution into the high-pressure reaction kettle to carry out copolymerization reaction of polyester-polycarbonate and polylactic acid in a nitrogen atmosphere;
(4) After the reaction is finished, the high-pressure reaction kettle is depressurized after being cooled to room temperature, and the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is obtained through dissolution, precipitation and drying.
5. The method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 4, wherein the pressure of the carbon dioxide gas in the step (2) is 0.2 to 5MPa, the reaction temperature is 40 to 70℃and the reaction time is 0.5 to 12 hours.
6. The method for preparing the carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2 or 4, wherein the mass fraction of phthalic anhydride in the carbon dioxide-based polyester-polycarbonate biodegradable copolymer is 10% -40%, the mass fraction of polycarbonate in the polymer is 10% -60%, the mass fraction of polyether in the polymer is less than 40%, and the mass fraction of polylactic acid in the polymer is 5% -40%.
7. The method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2 or 4, wherein the molar ratio of the lewis base catalyst to the organoborane is 1:0.5-8, the molar feed ratio of Lewis base catalyst to phthalic anhydride is 1:50-5000, the molar feed ratio of phthalic anhydride to propylene oxide is 1:2-100, wherein the molar feed ratio of polylactic acid to phthalic anhydride is 1:2-200.
8. The method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2 or 4, wherein the lewis base is tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, triethyl methyl ammonium chloride, bis (triphenylphosphine) ammonium chloride, benzyl trimethyl ammonium chloride or benzyl triethyl ammonium chloride; the organoborane is triethylboron, tripropylboron, tributylboron, tribenzylboron, trimethylamineboronic or dimethylamine boron.
9. The method for producing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2 or 4, wherein the organic solvent is ethylene oxide or tetrahydrofuran.
10. The method for preparing a carbon dioxide-based polyester-polycarbonate biodegradable copolymer according to claim 2 or 4, wherein the polylactic acid has a weight average molecular weight of 20,000 to 500,000g/mol, including PLLA or PDLA.
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