CN113493598A - Biodegradable polyester and preparation method thereof - Google Patents
Biodegradable polyester and preparation method thereof Download PDFInfo
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- CN113493598A CN113493598A CN202110935089.0A CN202110935089A CN113493598A CN 113493598 A CN113493598 A CN 113493598A CN 202110935089 A CN202110935089 A CN 202110935089A CN 113493598 A CN113493598 A CN 113493598A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- 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
Abstract
The invention provides a biodegradable polyester and a preparation method thereof. The biodegradable polyester provided by the invention is prepared from the following raw materials in parts by weight: 160-480 parts of a PET material, 85-260 parts of poly (carbonate-ether) dihydric alcohol, 0.3-18 parts of poly (carbonate-ether) polyhydric alcohol, 16-115 parts of dibasic acid, 0.08-0.5 part of antioxidant and 0.2-1.6 parts of catalyst. The invention takes the waste PET as the raw material, and simultaneously introduces other raw materials to successfully synthesize the biodegradable polyester, thereby not only completing the chemical recovery of the waste PET, but also leading the obtained material to be biodegradable and having good mechanical property.
Description
Technical Field
The invention relates to the field of organic materials, in particular to biodegradable polyester and a preparation method thereof.
Background
In 2018, global polyethylene terephthalate (PET) production was as high as 7968 million tons, while on average, it was still rapidly increasing at a rate of 8.5% per year. However, PET is difficult to degrade in nature, and landfill or incineration disposal imposes a great pressure on the environment, and a great amount of waste PET needs to be recycled.
The recycling method of the waste PET polyester material comprises a physical method and a chemical method. The physical method mainly adopts mechanical processing to obtain low-value chemicals, and the economical efficiency is poor. Thus, chemical processes have become the primary method for recycling waste PET polyester materials, depolymerizing them into monomers or other oligomers, and further processing for use. In 2002, the japanese imperial company developed a process for producing dimethyl terephthalate (DMT) and Ethylene Glycol (EG) from PET bottles by a chemical recovery method, in which PET chips were dispersed in ethylene glycol, depolymerized at 198 ℃ to bishydroxyethyl terephthalate, and then subjected to a transesterification reaction with methanol at 65 ℃ to produce DMT and EG, followed by recrystallization to obtain DMT, and then EG was recovered by distillation. At present, all PET chemical recycling is prepared into micromolecular DMT monomers, and efficient recycling with high added value cannot be obtained.
The yield of plastic products in 1990 in China is only 550 ten thousand tons, and the yield of the plastic products in 2019 in China reaches 8184 ten thousand tons, which is increased by 3.91 percent on a same scale. However, after a large amount of plastic products are used and discarded, the plastic products cannot be degraded and recycled, so that the environment is polluted greatly, the problem becomes a hot spot of global attention, and the biodegradable plastic becomes a development trend in the field in recent years. According to data published by the European bioplastic society in 2019 and 9 months, the annual capacity of global bioplastic is 211.4 ten thousand tons, wherein the percentage of biodegradable plastic (including poly adipate-butylene glycol terephthalate (PBAT), Poly Butylene Succinate (PBS), polylactic acid (PLA), Polyhydroxyalkanoate (PHA), starch-based degradable plastic and the like) is 55.5% and 117.4 ten thousand tons, and the annual capacity of global biodegradable plastic is expected to reach 133.4 ten thousand tons and the annual composite growth rate is 2.7% by 2024 years.
Although the biodegradable material can alleviate the problem of white pollution, the raw materials of the biodegradable material are almost all derived from a large amount of petrochemical resources, and the research on the preparation of the biodegradable plastic by a method which does not completely depend on the petrochemical resources is a research difficulty in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a biodegradable polyester and a preparation method thereof. According to the biodegradable polyester and the preparation method thereof provided by the invention, the waste PET is used as a raw material, so that the chemical recovery of the waste PET is completed, the obtained material is biodegradable, and the material has good mechanical properties.
The invention provides biodegradable polyester which is prepared from the following raw materials in parts by weight:
preferably, the number average molecular weight of the poly (carbonate-ether) glycol is 3300-6000 g/mol, and the carbonate unit content is 30 wt% -55 wt%.
Preferably, the poly (carbonate-ether) polyol is selected from one or more of poly (carbonate-ether) polyols having a hydroxyl functionality of 6 and a hydroxyl functionality of 4.
Preferably, the poly (carbonate-ether) polyol having a hydroxyl functionality of 6 has a number average molecular weight of 1600 to 7900g/mol and a carbonate unit content of 40 to 51 wt%.
Preferably, the poly (carbonate-ether) polyol having a hydroxyl functionality of 4 has a number average molecular weight of 1500 to 3050g/mol and a carbonate unit content of 32 to 46 wt%.
Preferably, the dibasic acid is one or more selected from C3-C16 alkyl dibasic acids.
Preferably, the dibasic acid is selected from one or more of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, 1, 15-pentadecanedioic acid and 1, 16-hexadecanedioic acid;
the catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, diethyl zinc, zinc octoate, zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, zinc oxide and zinc chloride;
the antioxidant is selected from one or more of triethyl phosphite, pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
The invention also provides a preparation method of the biodegradable polyester in the technical scheme, which comprises the following steps:
a) mixing and reacting a PET material, poly (carbonate-ether) dihydric alcohol, a catalyst and an antioxidant to obtain a first intermediate;
b) mixing the first intermediate and poly (carbonate-ether) polyol for reaction to obtain a second intermediate;
c) and mixing the second intermediate and dibasic acid for reaction to obtain the biodegradable polyester.
Preferably, in the step a), the reaction temperature is 140-180 ℃ and the reaction time is 0.5-3.5 h;
in the step b), the reaction temperature is 200-220 ℃, and the reaction time is 0.5-2.5 h;
in the step c), the reaction temperature is 230-270 ℃ and the reaction time is 3.5-8.5 h.
Preferably, the step c) comprises: heating the system to 230-270 ℃, adding dibasic acid, and reacting for 1-2 hours; then, vacuumizing the system, reducing the pressure to a first pressure, and reacting for 0.5-1.5 h; then, continuously vacuumizing and reducing the pressure to a second pressure, and reacting for 2-5 h; the first pressure is 800-2000 Pa; the second pressure is 30-100 Pa.
The biodegradable polyester provided by the invention is successfully synthesized by taking a PET material, degradable poly (carbonate-ether) dihydric alcohol and poly (carbonate-ether) polyhydric alcohol as raw materials and adding dibasic acid, an antioxidant and a catalyst, so that not only is the chemical recovery of waste PET completed, but also the obtained material is biodegradable, a new thought is provided for the chemical recovery of the waste PET material, and a new technical scheme is provided for the synthesis of novel biodegradable polyester. Meanwhile, the obtained biodegradable polyester has good tensile property and can be used in the fields of mulching films, bubble bags, vest bags and the like.
Experimental results show that after the biodegradable polyester material provided by the invention is degraded for 45 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are both obviously reduced, and the molecular weight distribution breadth index (pdi) is narrowed, which shows that the material is effectively degraded to generate a micromolecular product. The biodegradation result shows that after 20 days, the material is disintegrated, and the degradation rate is 55-65%; the degradation rate is 82% -92% after 90 days; the degradation rate is 95% -98% in 180 days, and the material is further verified to have excellent degradation performance. The mechanical property result shows that the elongation at break of the material is more than 410 percent, and the tensile strength is more than 14.5MPa, and the result shows that the material has excellent tensile mechanical property.
Detailed Description
The invention provides biodegradable polyester which is prepared from the following raw materials in parts by weight:
the biodegradable polyester provided by the invention takes PET material, degradable poly (carbonate-ether) dihydric alcohol and poly (carbonate-ether) polyhydric alcohol as raw materials, and is matched with the other components to successfully synthesize the biodegradable polyester, so that not only can the chemical recovery of waste PET be completed, but also the obtained material can be biodegraded, and a new thought is provided for the chemical recovery of the waste PET material; meanwhile, the obtained biodegradable polyester has good tensile property and can be used in the fields of mulching films, bubble bags, vest bags and the like.
According to the invention, the PET (i.e. polyethylene terephthalate) material is preferably waste PET material, such as waste products of beverage bottles, transparent packaging boxes and the like. Before preparation, the waste PET material is crushed into pieces in advance, or if the waste PET material is originally fragments, the waste PET material can be directly used.
In the invention, the amount of the PET material is 160-480 parts; in some embodiments of the invention, it is used in an amount of 160 parts, 285 parts, 300 parts, 350 parts, 420 parts, 460 parts, or 480 parts.
According to the invention, the poly (carbonate-ether) diol is a polymer containing 2 hydroxyl functional groups, in particular a polymer containing 2 terminal hydroxyl functional groups. In the present invention, the kind of the poly (carbonate-ether) glycol is preferably: a poly (carbonate-ether) glycol having a number average molecular weight of 3300 to 6000g/mol and a carbonate unit content of 30 wt% to 55 wt%. In some embodiments of the invention, the poly (carbonate-ether) glycol is selected from one or more of the following classes: the number-average molecular weight Mn is 6000g/mol, and the carbonate unit content is 34.3%; or the number average molecular weight Mn is 3300g/mol, the carbonate unit content is 30.6%; or the number average molecular weight Mn is 3500g/mol, and the content of carbonate units is 54.8 percent; or a number-average molecular weight Mn of 5800g/mol and a carbonate unit content of 35.2%.
In the present invention, the poly (carbonate-ether) glycol is preferably prepared by the following preparation method: carbon dioxide and an epoxy compound are polymerized in the presence of a chain transfer agent in the presence of a catalyst to form a poly (carbonate-ether) glycol. Wherein the epoxy compound is an alkylene oxide or a halogenated alkylene oxide; preferably one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide and epichlorohydrin. More specifically, the poly (carbonate-ether) diol is preferably prepared according to the method reported in patent application 201110231493.6.
In the invention, the amount of the poly (carbonate-ether) glycol is 85-260 parts based on 160-480 parts of the amount of the PET material; in some embodiments of the present invention, the poly (carbonate-ether) glycol is used in an amount of 85 parts, 102 parts, 135 parts, 210 parts, 235 parts, 255 parts, or 260 parts.
According to the present invention, the poly (carbonate-ether) polyol refers to a polymer having a hydroxyl functionality of 3 or more; in the present invention, the poly (carbonate-ether) polyol is selected from one or more of poly (carbonate-ether) polyols having a hydroxyl functionality of 6 and a hydroxyl functionality of 4. Wherein 4 hydroxyl groups in the poly (carbonate-ether) polyol having a functionality of 4 are terminal hydroxyl groups. In the poly (carbonate-ether) polyol having a hydroxyl functionality of 6, 4 or 6 hydroxyl groups are terminal hydroxyl groups.
In the present invention, the type of poly (carbonate-ether) polyol having a hydroxyl functionality of 6 is preferably: a poly (carbonate-ether) polyol having a number average molecular weight of 1600 to 7900g/mol and a carbonate unit content of 40 to 51 wt%. In some embodiments of the present invention, the poly (carbonate-ether) polyol having a hydroxyl functionality of 6 is selected from one or more of the following classes: the number-average molecular weight Mn is 7900g/mol, and the carbonate unit content is 50.8%; or the number average molecular weight Mn is 1600g/mol, and the content of carbonate units is 40.7 percent; or a number-average molecular weight Mn of 3000g/mol and a carbonate unit content of 46.6%. In the present invention, the poly (carbonate-ether) polyol having a hydroxyl functionality of 6 is preferably prepared according to the preparation method reported in the prior art "controlled synthesis of carbon dioxide-based hexahydric alcohol having a branched structure, King-Dong red et al, published in macromolecules 2017, 2: 259-265".
In the present invention, the type of the poly (carbonate-ether) polyol having a hydroxyl functionality of 4 is preferably: a poly (carbonate-ether) polyol having a number average molecular weight of 1500 to 3050g/mol and a carbonate unit content of 32 to 46 wt%. In some embodiments of the present invention, the poly (carbonate-ether) polyol having a hydroxyl functionality of 4 is selected from one or more of the following classes: the number-average molecular weight Mn is 2000g/mol, the carbonate unit content is 36.9%; or the number-average molecular weight Mn is 3050g/mol, and the content of carbonate units is 32.7 percent; or a number-average molecular weight Mn of 1500g/mol and a carbonate unit content of 45.2%. In the present invention, the poly (carbonate-ether) polyol having a hydroxyl functionality of 4 is preferably prepared according to the prior art "Controllable synthesis of a narrow polydispersity CO2Prepared by the preparation method reported in-based oligo (carbonate-ether) tetraol, wang et al, Polymer. chem.,2015,6,7580-7585 ".
In the invention, the amount of the poly (carbonate-ether) polyol is 0.3-18 parts, preferably 0.35-17.8 parts, based on 160-480 parts of the PET material; in some embodiments of the present invention, the poly (carbonate-ether) polyol is used in an amount of 0.35 parts, 4.5 parts, 5.8 parts, 13.6 parts, 14.6 parts, 16.8 parts, or 17.8 parts.
According to the invention, the dibasic acid is micromolecular dibasic acid, and is specifically selected from one or more of C3-C16 alkyl dibasic acids; more preferably one or more of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, 1, 15-pentadecanedioic acid, and 1, 16-hexadecanedioic acid.
According to the invention, the use amount of the PET material is 160-480 parts as a reference, and the use amount of the dibasic acid is 16-115 parts; in some embodiments of the invention, the amount of the dibasic acid is 16 parts, 62 parts, 65 parts, 85 parts, 105 parts, 107 parts, or 115 parts.
According to the invention, the antioxidant is preferably one or more of triethyl phosphite, pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; more preferably one or two of the above.
According to the invention, the amount of the antioxidant is 0.08-0.5 part, preferably 0.08-0.42 part based on 160-480 parts of the amount of the PET material; in some embodiments of the invention, the antioxidant is used in an amount of 0.08 parts, 0.16 parts, 0.26 parts, 0.32 parts, 0.36 parts, 0.38 parts, or 0.42 parts.
According to the invention, the catalyst is preferably one or more of tetrabutyl titanate, tetraisopropyl titanate, diethyl zinc, zinc octoate, zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, zinc oxide and zinc chloride.
In the invention, the amount of the catalyst is 0.2-1.6 parts, preferably 0.22-1.58 parts, based on 160-480 parts of the PET material; in some embodiments of the invention, the catalyst is used in an amount of 0.22 parts, 0.95 parts, 1.08 parts, 1.15 parts, 1.25 parts, 1.46 parts, or 1.58 parts.
The invention also provides a preparation method of the biodegradable polyester in the technical scheme, which comprises the following steps:
a) mixing and reacting a PET material, poly (carbonate-ether) dihydric alcohol, a catalyst and an antioxidant to obtain a first intermediate;
b) mixing the first intermediate and poly (carbonate-ether) polyol for reaction to obtain a second intermediate;
c) and mixing the second intermediate and dibasic acid for reaction to obtain the biodegradable polyester.
The types, the amounts and the like of the PET material, the poly (carbonate-ether) dihydric alcohol, the poly (carbonate-ether) polyhydric alcohol, the dibasic acid, the catalyst and the antioxidant are consistent with those in the technical scheme, and are not repeated here.
With respect to step a): mixing and reacting a PET material, poly (carbonate-ether) dihydric alcohol, a catalyst and an antioxidant to obtain a first intermediate.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The type of gas used to provide the protective atmosphere is not particularly limited in the present invention and may be any conventional protective gas known to those skilled in the art, such as nitrogen, helium, argon, or the like. The pressure of the protective atmosphere is not particularly limited, and the protective atmosphere is normal pressure, namely the reaction is carried out under normal pressure.
In the invention, the reaction temperature is preferably 140-180 ℃; in some embodiments of the invention, the reaction temperature is 140 ℃, 150 ℃, 160 ℃, 170 ℃, 175 ℃ or 180 ℃. The reaction time is preferably 0.5-3.5 h; in some embodiments of the invention, the reaction time is 0.5h, 1h, 2h, 2.5h, or 3.5 h. In the present invention, stirring is preferably carried out during the reaction.
In the reaction process, the terminal hydroxyl in the structure of the poly (carbonate-ether) glycol and the PET material (ethylene terephthalate) are subjected to ester exchange reaction, and the PET material is synthesized into a hydroxyl-terminated poly (carbonate-ether) glycol-terephthalic acid-ethylene glycol copolymer, namely a first intermediate.
In the invention, the antioxidant is added to delay or inhibit the polymer oxidation process in the polymerization process and prevent the polymer byproduct, and the addition in the step a) can ensure that the product obtains the best performance. After the antioxidant is added in the step a), the generation of byproducts caused by high temperature (140-180 ℃) in the PET alcoholysis process can be prevented, if the antioxidant is added in the step b) or the step c), more byproducts are generated in the step b) and the step c) due to the generation of byproducts with hydroxyl and carboxyl cross-linked structures and dioxide, so that the molecular weight of the product is smaller, the color is increased, and the product performance is reduced.
With respect to step b): and mixing the first intermediate and the poly (carbonate-ether) polyol for reaction to obtain a second intermediate.
In the invention, the reaction temperature is preferably 200-220 ℃; in some embodiments of the invention, the reaction temperature is 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃. The reaction time is preferably 0.5-2.5 h; in some embodiments of the invention, the reaction time is 0.5h, 1h, or 1.5 h.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The type of gas used to provide the protective atmosphere is not particularly limited in the present invention and may be any conventional protective gas known to those skilled in the art, such as nitrogen, helium, argon, or the like. The pressure of the protective atmosphere is not particularly limited, and the protective atmosphere is normal pressure, namely the reaction is carried out under normal pressure. Specifically, after the reaction in step a) is finished, the temperature of the system is continuously raised to the target reaction temperature, and the poly (carbonate-ether) polyol is added for reaction.
During the above reaction, the first intermediate is further transesterified with the terminal hydroxyl groups of the poly (carbonate-ether) polyol (4 or 6 functional hydroxyl groups) to produce a poly (carbonate-ether) diol-terephthalic acid-ethylene glycol copolymer having a crosslinked structure, i.e., a second intermediate.
With respect to step c): and mixing the second intermediate and dibasic acid for reaction to obtain the biodegradable polyester.
In the invention, the reaction temperature is preferably 230-270 ℃; in some embodiments of the invention, the reaction temperature is 230 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃. The reaction time is preferably 3.5-8.5 h; in some embodiments of the invention, the reaction time is 3.5h, 5h, 5.5h, 6.5h, or 8.5 h.
The reaction process is preferably as follows: heating the system to 230-270 ℃, adding dibasic acid, and reacting for 1-2 hours; then, vacuumizing the system, reducing the pressure to a first pressure, and reacting for 0.5-1.5 h; and then, continuously vacuumizing and reducing the pressure to a second pressure, and reacting for 2-5 h. Wherein the first pressure is 800-2000 Pa, preferably 1000 Pa. The second pressure is 30-100 Pa, preferably 50 Pa.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The type of gas used to provide the protective atmosphere is not particularly limited in the present invention and may be any conventional protective gas known to those skilled in the art, such as nitrogen, helium, argon, or the like. The pressure of the protective atmosphere is not particularly limited, and the protective atmosphere is normal pressure, namely the reaction is carried out under normal pressure. Namely, the same atmosphere condition is maintained as that of the steps a) to b), specifically, after the reaction of the step b) is finished, the temperature of the system is directly increased to the target reaction temperature, and the dibasic acid is added for reaction.
In the above reaction process, the hydroxyl group of the second intermediate with a terminal hydroxyl group structure and dibasic acid are subjected to esterification reaction and further polycondensation to form a high molecular poly (carbonate-ether) glycol-terephthalic acid-ethylene glycol copolymer, i.e. biodegradable polyester.
In the preparation process of the above steps a) to c), the addition and the reaction are carried out according to a specific addition sequence, and although the addition is carried out on the poly (carbonate-ether) alcohol substances, the poly (carbonate-ether) dihydric alcohol is added firstly, and then the poly (carbonate-ether) polyhydric alcohol is added. On the one hand, the hydroxyl group of the poly (carbonate-ether) diol has less steric hindrance than the terminal hydroxyl group of the poly (carbonate-ether) polyol, and the alcoholysis reaction of the PET material can be carried out more easily after the poly (carbonate-ether) diol is added, so that the alcoholysis efficiency is low and more PET materials cannot be subjected to effective alcoholysis. On the other hand, when the steps are reversed, the poly (carbonate-ether) polyol with polyhydroxy functionality is used for alcoholysis of PET, and the generated copolymer component with a cross-linked structure has a very high viscosity, which is more unfavorable for the next transesterification reaction of the poly (carbonate-ether) diol. Therefore, the invention controls PET to react with dihydric alcohol and then with polyhydric alcohol, otherwise, biodegradable polyester with high molecular weight cannot be obtained.
The biodegradable polyester provided by the invention is successfully synthesized by taking a PET material, degradable poly (carbonate-ether) dihydric alcohol and poly (carbonate-ether) polyhydric alcohol as raw materials and adding dibasic acid, an antioxidant and a catalyst, so that not only is the chemical recovery of waste PET completed, but also the obtained material is biodegradable, a new thought is provided for the chemical recovery of the waste PET material, and a new technical scheme is provided for the synthesis of novel biodegradable polyester. Meanwhile, the obtained biodegradable polyester has good tensile property and can be used in the fields of mulching films, bubble bags, vest bags and the like.
Experimental results show that after the biodegradable polyester material provided by the invention is degraded for 45 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are both obviously reduced, and the molecular weight distribution breadth index (pdi) is narrowed, which shows that the material is effectively degraded to generate a micromolecular product. The biodegradation result shows that after 20 days, the material is disintegrated, and the degradation rate is 55-65%; the degradation rate is 82% -92% after 90 days; the degradation rate is 95% -98% in 180 days, and the material is further verified to have excellent degradation performance. The mechanical property result shows that the elongation at break of the material is more than 410 percent, and the tensile strength is more than 14.5MPa, and the result shows that the material has excellent mechanical property.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, "Cu%" refers to the amount of carbonate units in the corresponding poly (carbonate-ether) diol or poly (carbonate-ether) polyol.
Example 1
S1, 160g of waste PET, 85g of poly (carbonate-ether) glycol (Mn 3300g/mol, Cu%: 30.6%), 0.22g of tetrabutyl titanate, and 0.08g of triethyl phosphite were sequentially charged into a reaction vessel under nitrogen protection, and after the temperature was raised to 140 ℃, stirring was started, and the reaction was carried out for 2.5 hours, thereby obtaining a first intermediate.
S2, the system was further warmed to 200 ℃, 0.35g of poly (carbonate-ether) tetrahydric alcohol (Mn 2000g/mol, Cu% 36.9%) was added to the first intermediate, and the reaction was carried out for 1.5 hours to obtain a second intermediate.
S3, continuously heating the system to 230 ℃, adding 16g of 1, 3-malonic acid, continuously reacting for 2 hours, vacuumizing and reducing the pressure of the system to 1000Pa, reacting for 1.5 hours, continuously vacuumizing and reducing the pressure, controlling the negative pressure to 50Pa, reacting for 5 hours, and stopping the reaction, wherein the acid value is less than or equal to 3 mgKOH/g. And continuously extruding the reaction product from the bottom of the polymerization kettle, cooling and pelletizing.
Example 2
S1, 480g of waste PET, 260g of poly (carbonate-ether) diol (Mn 6000g/mol, Cu%: 34.3%), 1.58g of tetraisopropyl titanate, and 0.42g of pentaerythritol diphosphite were sequentially charged into a reaction vessel under nitrogen protection, and after the temperature was increased to 180 ℃, stirring was started, and the reaction was carried out for 0.5 hour to obtain a first intermediate.
S2, the temperature was raised to 220 ℃, 17.8g of poly (carbonate-ether) hexahydric alcohol (Mn 7900g/mol, Cu% 50.8%) was added to the first intermediate, and the reaction was carried out for 0.5 hour to obtain a second intermediate.
And S3, continuously raising the temperature to 270 ℃, adding 115g of 1, 4-succinic acid, continuously reacting for 1 hour, vacuumizing and decompressing until the system pressure is 1000Pa, reacting for 0.5 hour, continuously vacuumizing and decompressing, controlling the negative pressure at 50Pa, reacting for 2 hours, continuously extruding the reaction product from the bottom of the polymerization kettle, cooling and pelletizing, wherein the acid value is less than or equal to 3 mgKOH/g.
Example 3
S1, under nitrogen protection, 300g of waste PET, 135g of poly (carbonate-ether) diol (Mn 3500g/mol, Cu 54.8%), 0.95g of diethyl zinc, and 0.16g of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite were sequentially charged into a reaction vessel, and after the temperature was raised to 150 ℃, stirring was started, and the reaction was carried out for 1 hour, thereby obtaining a first intermediate.
S2, the temperature was raised to 210 ℃, 4.5g of poly (carbonate-ether) tetrahydric alcohol (Mn 3050g/mol, Cu%: 32.7%) was added to the first intermediate, and the reaction was carried out for 1 hour to obtain a second intermediate.
And S3, continuously raising the temperature to 250 ℃, adding 62g of 1, 6-adipic acid, continuously reacting for 1.5 hours, vacuumizing and reducing the pressure of the system to 1000Pa, reacting for 1 hour, continuously vacuumizing and reducing the pressure, controlling the negative pressure to be 50Pa, reacting for 2.5 hours, stopping the reaction, continuously extruding the reaction product from the bottom of a polymerization kettle, cooling and pelletizing.
Example 4
S1, under nitrogen protection, 350g of waste PET, 210g of poly (carbonate-ether) diol (Mn 3500g/mol, Cu 54.8%), 1.08g of zinc octoate, and 0.32g of dioctadecyl pentaerythritol diphosphite were sequentially charged into a reaction vessel, and the temperature was increased to 160 ℃, followed by stirring and reaction for 2 hours, thereby obtaining a first intermediate.
S2, the temperature was raised to 215 ℃, 13.6g of poly (carbonate-ether) hexahydric alcohol (Mn 1600g/mol, Cu 40.7%) was added to the first intermediate, and the reaction was carried out for 1 hour to obtain a second intermediate.
S3, continuously raising the temperature to 250 ℃, adding 85g of 1, 7-pimelic acid, continuously reacting for 1.5 hours, vacuumizing and reducing the pressure of the system to 1000Pa, reacting for 1 hour, continuously vacuumizing and reducing the pressure, controlling the negative pressure to be 50Pa, reacting for 3 hours, stopping the reaction, continuously extruding the reaction product from the bottom of the polymerization kettle, cooling and pelletizing.
Example 5
S1, under nitrogen protection, 420g of waste PET, 235g of poly (carbonate-ether) diol (Mn 5800g/mol, Cu%: 35.2%), 1.25g of manganese acetate, and 0.36g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester were sequentially charged into a reaction vessel, and after the temperature was increased to 170 ℃, stirring was started, and the reaction was carried out for 3.5 hours, thereby obtaining a first intermediate.
S2, the temperature was raised to 205 ℃, 5.8g of poly (carbonate-ether) tetrahydric alcohol (Mn 3050g/mol, Cu%: 32.7%) was added to the first intermediate, and the reaction was carried out for 1.5 hours to obtain a second intermediate.
S3, continuously raising the temperature to 260 ℃, adding 107g of 1, 9-azelaic acid, continuously reacting for 1.5 hours, vacuumizing and reducing the pressure of the system to 1000Pa, reacting for 1 hour, continuously vacuumizing and reducing the pressure, controlling the negative pressure to be 50Pa, reacting for 4 hours, stopping the reaction, continuously extruding the reaction product from the bottom of a polymerization kettle, cooling and pelletizing.
Example 6
S1, under nitrogen protection, 285g of waste PET, 102g of poly (carbonate-ether) diol (Mn 3300g/mol, Cu% 30.6%), 1.15g of zinc phosphate, and 0.26g of pentaerythritol diphosphite were sequentially charged into a reaction vessel, and after the temperature was raised to 175 ℃, stirring was started, and a reaction was carried out for 2 hours, thereby obtaining a first intermediate.
S2, the temperature was raised to 215 ℃, 14.6g of poly (carbonate-ether) hexahydric alcohol (Mn 3000g/mol, Cu% 46.6%) was added to the first intermediate, and the reaction was carried out for 1 hour to obtain a second intermediate.
And S3, continuously raising the temperature to 255 ℃, adding 65g of 1, 12-dodecanedioic acid, continuously reacting for 1.5 hours, vacuumizing and decompressing to 1000Pa of system pressure, reacting for 0.5 hour, continuously vacuumizing and decompressing, controlling the negative pressure to 50Pa, reacting for 4.5 hours, stopping the reaction, continuously extruding the reaction product from the bottom of a polymerization kettle, cooling and pelletizing.
Example 7
S1, under nitrogen protection, 460g of waste PET, 255g of poly (carbonate-ether) diol (Mn 5800g/mol, Cu%: 35.2%), 1.46g of zinc oxide, and 0.38g of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine were sequentially charged into a reaction vessel, and after the temperature was raised to 175 ℃, stirring was started, and the reaction was carried out for 2 hours, thereby obtaining a first intermediate.
S2, the temperature was raised to 220 ℃, 16.8g of poly (carbonate-ether) tetrahydric alcohol (Mn 1500g/mol, Cu 45.2%) was added to the first intermediate, and the reaction was carried out for 1.5 hours to obtain a second intermediate.
And S3, continuously raising the temperature to 265 ℃, adding 105g of 1, 16-hexadecanedioic acid, continuously reacting for 1.5 hours, vacuumizing and reducing the pressure to 1000Pa, reacting for 1 hour, continuously performing negative pressure, controlling the negative pressure to be 50Pa, reacting for 4 hours, continuously extruding a reaction product from the bottom of a polymerization kettle, cooling and pelletizing, wherein the acid value is less than or equal to 3 mgKOH/g.
Example 8: performance testing
The polyester products obtained in examples 1 to 7 were subjected to performance tests, and the results are shown in Table 1.
1. Change of molecular weight:
the molecular weight change of the material, including the molecular weight before and after degradation and the molecular weight change, was tested by GPC with tetrahydrofuran as the mobile phase. Degradation for 45 days was carried out according to the method GB/T19277.1-2011.
2. And (3) testing the biodegradation condition: the material was made into a film with a thickness of 120 microns and tested according to GB/T19277.1-2011. In a 2L test system, the test mixture was aerated at a controlled rate with carbon dioxide free air using the material of the present invention as an organic carbon source. The degradation rate was determined by measuring the amount of carbon dioxide produced. 240g of culture soil was mixed with 40g of the polyester material obtained in the examples of the present invention and 40g of microcrystalline cellulose, respectively, and 240g of culture soil was used as a blank control, and distilled water was added to adjust the humidity of the mixture to about 50%. Placing the compost container in a test environment at (58 +/-2) DEG C and using CO-free2The test system was aerated at a flow rate of 0.05L/min with saturated air at a temperature of (58. + -. 2) ℃ and the test was carried out. The biodegradation rate of the test material was determined as the ratio of the amount of carbon dioxide actually produced by the test material during the test to the theoretical amount of carbon dioxide released from the test material.
3. And (3) testing mechanical properties:
the material before degradation is made into a dumbbell shape, and a tensile test is carried out at room temperature of 25 ℃ by a universal tensile machine, wherein the tensile speed is 10 mm/min.
TABLE 1 Properties of polyester products obtained in examples 1 to 7
Note: in Table 1 above, the numerical units of the number average molecular weight Mn and the weight average molecular weight Mw are kg/mol; pdi refers to the polymer dispersity index (or breadth of molecular weight distribution index).
As can be seen from the test results in Table 1, after the material is degraded for 45 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) both show obvious reduction, and the molecular weight distribution breadth index (pdi) becomes narrow, which indicates that the material is effectively degraded to generate a small molecular product. The biodegradation result shows that after 20 days, the material is disintegrated, and the degradation rate is 55-65%; the degradation rate is 82% -92% after 90 days; the degradation rate is 95% -98% in 180 days, and the material is further verified to have excellent degradation performance. The mechanical property result shows that the elongation at break of the material is more than 410 percent, and the tensile strength is more than 14.5MPa, and the result shows that the material has excellent mechanical property and can be used in the fields of mulching films, bubble bags, vest bags and the like.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The biodegradable polyester is characterized by being prepared from the following raw materials in parts by weight:
2. the biodegradable polyester according to claim 1, wherein the number average molecular weight of the poly (carbonate-ether) glycol is 3300-6000 g/mol, and the carbonate unit content is 30-55 wt%.
3. Biodegradable polyester according to claim 1, characterized in that said poly (carbonate-ether) polyol is selected from one or more of poly (carbonate-ether) polyols having a hydroxyl functionality of 6 and a hydroxyl functionality of 4.
4. The biodegradable polyester according to claim 3, wherein the poly (carbonate-ether) polyol with a hydroxyl functionality of 6 has a number average molecular weight of 1600 to 7900g/mol and a carbonate unit content of 40 to 51 wt.%.
5. The biodegradable polyester according to claim 3, wherein the poly (carbonate-ether) polyol having a hydroxyl functionality of 4 has a number average molecular weight of 1500 to 3050g/mol and a carbonate unit content of 32 to 46 wt%.
6. The biodegradable polyester according to claim 1, wherein the dibasic acid is selected from one or more of C3-C16 alkyl dibasic acids.
7. Biodegradable polyester according to claim 1 or 6, characterized in that said diacid is selected from one or several of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, 1, 15-pentadecanedioic acid and 1, 16-hexadecanedioic acid;
the catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, diethyl zinc, zinc octoate, zinc acetate, manganese phosphate, zinc phosphate, calcium phosphate, zinc oxide and zinc chloride;
the antioxidant is selected from one or more of triethyl phosphite, pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
8. A method for preparing the biodegradable polyester according to any one of claims 1 to 7, comprising the steps of:
a) mixing and reacting a PET material, poly (carbonate-ether) dihydric alcohol, a catalyst and an antioxidant to obtain a first intermediate;
b) mixing the first intermediate and poly (carbonate-ether) polyol for reaction to obtain a second intermediate;
c) and mixing the second intermediate and dibasic acid for reaction to obtain the biodegradable polyester.
9. The preparation method according to claim 8, wherein in the step a), the reaction temperature is 140-180 ℃ and the reaction time is 0.5-3.5 h;
in the step b), the reaction temperature is 200-220 ℃, and the reaction time is 0.5-2.5 h;
in the step c), the reaction temperature is 230-270 ℃ and the reaction time is 3.5-8.5 h.
10. The method of claim 8, wherein the step c) comprises:
heating the system to 230-270 ℃, adding dibasic acid, and reacting for 1-2 hours; then, vacuumizing the system, reducing the pressure to a first pressure, and reacting for 0.5-1.5 h; then, continuously vacuumizing and reducing the pressure to a second pressure, and reacting for 2-5 h;
the first pressure is 800-2000 Pa;
the second pressure is 30-100 Pa.
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