CN113861399A - Biodegradable polyester PBIAT and preparation method thereof - Google Patents
Biodegradable polyester PBIAT and preparation method thereof Download PDFInfo
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- CN113861399A CN113861399A CN202111346243.7A CN202111346243A CN113861399A CN 113861399 A CN113861399 A CN 113861399A CN 202111346243 A CN202111346243 A CN 202111346243A CN 113861399 A CN113861399 A CN 113861399A
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- pbiat
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- isosorbide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 10
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 62
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000001361 adipic acid Substances 0.000 claims abstract description 31
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 21
- 229960002479 isosorbide Drugs 0.000 claims abstract description 21
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000005886 esterification reaction Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 238000004821 distillation Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000003208 petroleum Substances 0.000 abstract description 9
- 229920001896 polybutyrate Polymers 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 5
- 239000002689 soil Substances 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 18
- 238000005119 centrifugation Methods 0.000 description 9
- 229960001701 chloroform Drugs 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- -1 polybutylene succinate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010792 warming Methods 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
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 provides biodegradable polyester poly adipic acid-terephthalic acid-isosorbide-butylene glycol ester (PBIAT) and a preparation method thereof, belonging to the technical field of high polymer materials. The PBIAT polyester comprises the following components in percentage by mass: 27-23% of adipic acid, 31-26% of terephthalic acid, 6-48% of isosorbide and 36-3% of butanediol. The preparation method comprises the steps of uniformly mixing the adipic acid, the terephthalic acid, the isosorbide and the butanediol, adding the mixture into a reaction kettle for reaction, adding a catalyst, raising the temperature and carrying out polycondensation reaction to obtain the PBIAT polyester. The PBIAT polyester provided by the invention has good barrier property and excellent opening performance, and has better soil degradation speed, and better environmental friendliness and toughness compared with the traditional petroleum-based PBAT. The PBIAT polyester is synthesized by adopting an esterification-polycondensation polymerization technology, the yield is high, the preparation method is simple, the production process is easy to implement, and the environment is protected and saved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyester PBIAT and a preparation method thereof.
Background
With the progress of human society, high molecular materials are rapidly developed, are widely applied to various aspects of people's life, and become one of essential basic materials in modern life. The vast majority of polymer materials used today are derived from petrochemical resources and are therefore also referred to as petroleum-based polymer materials. In recent years, with the increasing demand for environmental protection and the continuous emphasis on sustainable development, the traditional petroleum-based polymer materials will face more and more severe situations and unprecedented challenges in development. The problem of white pollution generated after a large number of plastic products are used is mainly reflected, and particularly, the plastic products are difficult to degrade in the environment on disposable and difficult-to-recycle packaging materials used for a short time, so that the plastic products cause great harm to water bodies, soil and other resources depending on human survival; meanwhile, large-scale use of the petroleum chemical industry consumes a large amount of petrochemical resources, a large amount of carbon dioxide is discharged into the environment, global warming is accelerated, a series of serious consequences are brought, and the survival of various organisms on the earth and the development of human beings are threatened. Currently, biodegradable materials widely used globally mainly include polylactic acid (PLA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), poly (adipic acid/terephthalic acid-butylene glycol ester) (PBAT), polyoxyethylene-polyoxypropylene copolymer (PPC), Polycaprolactone (PCL), and the like. However, PBAT has the disadvantages of high production cost, poor openness, poor barrier property and the like, resulting in limited application fields, and still has certain limitations in terminal applications after modification, such as poor durability and economy, and meanwhile, increasingly severe environmental pollution, increasing scarcity of petroleum resources and continuous rising of prices thereof, and bring huge challenges to the petroleum-dependent polyester industry; the addition of isosorbide (a biomass derived by sorbitol dehydration) in PBIAT can well relieve the use of petroleum-based raw materials, and compared with the traditional degradable material, the PBIAT has more excellent barrier property and opening property, and especially compared with the traditional petroleum-based PBAT, the PBAT has more excellent soil degradation speed, environmental friendliness and toughness. The PBIAT polyester adopts esterification-polycondensation direct polymerization technology, has high yield, simple preparation method, easy implementation of production process, environmental protection and saving. Therefore, the PBIAT has excellent performance and high ecological friendliness, can replace general degradable materials such as PBAT, can be applied to the fields of disposable plastic straws, adhesive tapes, film products and the like, and is widely applied.
Disclosure of Invention
The invention aims to provide PBIAT and a preparation method thereof, and the PBIAT polyester has excellent comprehensive performance and simple preparation process. In order to achieve the above purpose, the invention provides the following technical scheme:
the invention firstly provides a bio-based degradable polyester PBIAT, which comprises the following components in percentage by mass: 27-23% of adipic acid, 31-26% of terephthalic acid, 6-48% of isosorbide and 36-3% of butanediol;
preferably, the molar ratio of the alcohol to the acid is (1.05:1) - (1.5: 1);
preferably, the molar ratio of isosorbide to butanediol in the alcohol is (1:9) - (9:1);
preferably, the molar ratio of terephthalic acid to adipic acid in the acid is (3:7) - (7:3);
preferably, the catalyst is tetrabutyl titanate;
preferably, the using amount of the tetrabutyl titanate is 0.1-0.5% of the total mass of the terephthalic acid and the adipic acid.
The invention also provides a preparation method of the PBIAT, which comprises the steps of weighing adipic acid, terephthalic acid, isosorbide and butanediol according to a proportion to prepare a mixed raw material, putting the mixed raw material into a reaction kettle, setting corresponding temperature and pressure to carry out esterification and polycondensation reaction, discharging, dissolving, extracting, centrifuging and drying after the reaction is finished to obtain a target product.
Preferably, the esterification temperature is 170-190 ℃, and the esterification time is 2-4 hours.
Preferably, the polycondensation temperature is 210-230 ℃ and the polycondensation time is 2-6 hours.
Preferably, the vacuum degree of the esterification reaction is-0.08 MPa to-0.13 MPa.
The invention has the advantages of
The invention firstly provides a biodegradable polyester PBIAT and a preparation method thereof, which comprises the following steps by weight percent: 27-23% of adipic acid, 31-26% of terephthalic acid, 6-48% of isosorbide and 36-3% of butanediol. Compared with the existing PBAT, the addition of isosorbide in the invention reduces the dependence on petroleum-based raw materials, improves the environmental friendliness of the materials, and simultaneously enables PBIAT to have higher soil degradation rate and better toughness on the premise of not sacrificing the original heat resistance and impact performance of PBAT.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention provides a bio-based degradable polyester PBIAT, which comprises the following components in molar ratio: the molar ratio of the alcohol to the acid is (1.05:1) - (1.5:1), preferably (1.1:1) - (1.4:1), and more preferably (1.15:1) - (1.3: 1).
Wherein the molar ratio of terephthalic acid to succinic acid in the acid is (3:7) - (7:3), preferably (3.5:6.5) - (6.5:3.5), more preferably (4:6) - (6:4), and the molar ratio of isosorbide to butanediol in the alcohol is (1:9) - (9:1), preferably (2:8) - (8:2), more preferably (3:7) - (7: 3).
The preparation method of the PBIAT polyester preferably comprises the following steps:
the temperature set for the esterification reaction is preferably 170-190 ℃, more preferably 175-185 ℃, and most preferably 180 ℃.
The esterification reaction time is preferably 2 to 4 hours, and most preferably 3 hours.
The temperature set for the polycondensation reaction is preferably 210 to 230 ℃, more preferably 215 to 225 ℃, and most preferably 220 ℃.
The polycondensation reaction time is preferably 2 to 6 hours, and most preferably 4 hours.
According to the invention, the catalyst is tetrabutyl titanate, and the dosage of the tetrabutyl titanate is preferably 0.1-0.5%, more preferably 0.2-0.4%, and most preferably 0.3%.
The raw material of the biodegradable polyester PBIAT according to the invention is a commercial product commonly used by those skilled in the art.
The present invention will be further illustrated in detail by the following examples, but it should be noted that these examples should not be construed as limiting the scope of the present invention in any way.
Example 1
Firstly, according to the invention, 3.887g of isosorbide, 21.575g of 1, 4-butanediol, 18.427g of the dicarboxylic acid and 16.210g of adipic acid are weighed, and 60g of the dicarboxylic acid and the adipic acid are fully dissolved and mixed uniformly in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and pausing the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 2
Firstly, according to the invention, 7.578g of isosorbide, 18.709g of 1, 4-butanediol and 60g of 17.961g of terephthalic acid and 15.799g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and pausing the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 3
Firstly, according to the invention, 11.092g of isosorbide, 15.960g of 1, 4-butanediol and 60g of 17.525g of terephthalic acid and 15.418g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 4
Firstly, according to the invention, 14.322g of isosorbide, 13.248g of 1, 4-butanediol and 60g of 16.965g of terephthalic acid and 14.923g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 5
Firstly, according to the invention, 17.661g of isosorbide, 10.891g of 1, 4-butanediol and 60g of 16.779g of terephthalic acid and 14.760g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 6
Firstly, according to the invention, 20.722g of isosorbide, 8.519g of 1, 4-butanediol and 60g of total 16.364g of the dicarboxylic acid and 14.395g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 7
Firstly, according to the invention, 23.324g of isosorbide, 6.250g of 1, 4-butanediol and 60g of 16.026g of terephthalic acid and 14.098g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 8
Firstly, according to the invention, 26.469g of isosorbide, 4.081g of 1, 4-butanediol and 60g of 15.676g of terephthalic acid and 13.790g of adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; after the reaction is finished, the product is poured into a beaker while the product is hot, is fully dissolved by trichloromethane, is extracted by cold methanol and is centrifuged, and after centrifugation, the supernatant is poured out and is dried in an oven at 60 ℃ for 24 hours to obtain PBIAT.
Example 9
Firstly, according to the invention, 28.748g of isosorbide, 1.998g of 1, 4-butanediol and 60g of 15.352g of the dimethyl acid and 13.505g of the adipic acid are weighed and fully dissolved and uniformly mixed in a beaker; putting the uniformly mixed monomers into a reaction kettle, setting the esterification reaction temperature to be 180 ℃, carrying out the whole esterification reaction under the nitrogen atmosphere, stopping introducing nitrogen until no water is generated, and suspending the reaction; cooling to below 100 ℃, adding a catalyst accounting for 0.3 percent of the total mass of the terephthalic acid and the adipic acid, wherein the catalyst is tetrabutyl titanate, sealing the reaction kettle again, setting the reaction temperature to be 220 ℃, introducing nitrogen for 2-3 minutes, starting first vacuumizing when the temperature is close to 220 ℃, slightly reducing the temperature at the moment, starting second vacuumizing when the temperature is close to 220 ℃ again to ensure that the vacuum degree is below-0.09 MPa, starting timing when the temperature is increased to 220 ℃, and reacting for 4 hours; and after the reaction is finished, pouring the hot product into a beaker, fully dissolving the product by using trichloromethane, extracting the product by using cold methanol, centrifuging the product, pouring out the supernatant after centrifugation, and drying the supernatant in an oven at 60 ℃ for 24 hours to obtain the PBIAT.
Claims (7)
1. A biodegradable polyester poly adipic acid-terephthalic acid-isosorbide-butylene glycol ester (PBIAT) and a preparation method thereof are characterized by comprising the following components in parts by weight: 27-23% of adipic acid, 31-26% of terephthalic acid, 6-48% of isosorbide and 36-3% of butanediol;
the preparation method of the PBIAT comprises the following steps:
a1, weighing adipic acid, terephthalic acid, isosorbide and butanediol according to a proportion to prepare a mixed raw material;
a2, putting the mixed raw materials into a reaction kettle, and setting corresponding temperature and pressure to carry out esterification and polycondensation reaction;
a3, discharging after the reaction is finished, dissolving, extracting, centrifuging and drying to obtain a target product;
in the step A2, the first-stage esterification reaction is carried out in nitrogen atmosphere, and a large amount of water is distilled in the esterification reaction process until the first-stage reaction is finished without water distillation; adding tetrabutyl titanate serving as a catalyst after the esterification is finished, stopping introducing nitrogen, continuously stirring, sealing the reaction kettle, raising the temperature to 220 ℃, pumping the pressure in the reaction kettle to be below-0.1 MPa by using a vacuum oil pump, keeping the vacuum degree, and starting the second-stage polycondensation reaction; and step A3, cooling to 60 ℃ after the polycondensation reaction is finished, discharging, adding a proper amount of chloroform into a beaker for dissolving, adding a proper amount of cold methanol for extraction after dissolving, pouring out supernatant liquor after centrifuging, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the PBIAT polyester.
2. The method for preparing the biodegradable polyester PBIAT as claimed in claim 1, wherein the molar ratio of the alcohol to the acid in the step A1 is (1.05:1) - (1.5: 1).
3. The method for preparing the biodegradable polyester PBIAT as claimed in claim 1, wherein in the step A1, the molar ratio of isosorbide to butanediol is (1:9) - (9: 1).
4. The method for preparing the biodegradable polyester PBIAT as claimed in claim 1, wherein in the step A1, the molar ratio of terephthalic acid to adipic acid is (3:7) - (7: 3).
5. The method for preparing PBIAT as claimed in claim 1, wherein in step A2, the esterification temperature is set at 170-190 ℃ and the reaction time is 2-4 hours.
6. The method for preparing PBIAT as claimed in claim 1, wherein in step A2, the temperature of polycondensation reaction is set at 210-230 ℃ for 2-6 hours.
7. The method for preparing biodegradable polyester PBIAT according to claim 1, wherein in the step A2, the catalyst selected by the polycondensation reaction is tetrabutyl titanate, and the dosage of the tetrabutyl titanate is 0.1-0.5% of the total mass of the terephthalic acid and the adipic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114752199A (en) * | 2022-05-31 | 2022-07-15 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
| CN114874599A (en) * | 2022-05-31 | 2022-08-09 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
| CN115011079A (en) * | 2022-05-31 | 2022-09-06 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
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| CN111087588A (en) * | 2019-12-18 | 2020-05-01 | 浙江恒澜科技有限公司 | Isosorbide modified high-heat-resistance biodegradable polyester and preparation method thereof |
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| CN114752199A (en) * | 2022-05-31 | 2022-07-15 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
| CN114874599A (en) * | 2022-05-31 | 2022-08-09 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
| CN115011079A (en) * | 2022-05-31 | 2022-09-06 | 东莞市惠国新材科技有限公司 | Polymer material and preparation method and application thereof |
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