CN115403749B - Degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester and preparation method thereof - Google Patents
Degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester and preparation method thereof Download PDFInfo
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 38
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 33
- 239000001361 adipic acid Substances 0.000 title claims abstract description 33
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 28
- 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 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000180 alkyd Polymers 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 230000009194 climbing Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- 239000005003 food packaging material Substances 0.000 claims description 3
- 229920001896 polybutyrate Polymers 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 13
- 229920000954 Polyglycolide Polymers 0.000 abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- -1 polybutylene adipate-butylene terephthalate Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229920002643 polyglutamic acid Polymers 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 20
- 239000000126 substance Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 10
- 239000004633 polyglycolic acid Substances 0.000 description 10
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 229920005604 random copolymer Polymers 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000229 biodegradable polyester Polymers 0.000 description 3
- 239000004622 biodegradable polyester Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920005586 poly(adipic acid) Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of degradable polyester synthesis, and particularly relates to degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester and a preparation method thereof. The method comprises the steps of firstly carrying out esterification reaction on adipic acid, terephthalic acid and 1,4 butanediol, adding an oligomer poly methyl glycolate and a catalyst into a reaction kettle together after the esterification of the monomers is finished, and then carrying out polycondensation reaction to obtain the poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester with high molecular weight. The copolyester of the invention has the performance advantages of polybutylene adipate-butylene terephthalate (PBAT) and Polyglycolide (PGA), has better oxygen and water vapor barrier performance and mechanical strength compared with PBAT, and has better flexibility compared with PGA. The copolyester has wide application prospect in the fields of high barrier requirements such as films, sheets, hollow containers and the like.
Description
Technical Field
The invention belongs to the field of degradable polyester synthesis, and particularly relates to degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester and a preparation method thereof.
Background
At present, the comprehensive performance of the biodegradable polyester poly (adipic acid)/poly (butylene terephthalate) (PBAT) is close to that of general plastic polyethylene, so that the biodegradable polyester poly (adipic acid)/poly (butylene terephthalate) (PBAT) becomes one of three important biodegradable materials which are mainly developed worldwide, the productivity is rapidly increased, and the maximum worldwide PBAT production enterprise is Basoff (BASF) in Germany, and the annual yield is 7.4 ten thousand tons. Although PBAT is the largest share of its application in replacing traditional film bags and packaging, its further development is limited by the drawbacks of higher production cost, poor barrier properties, low tear strength, insufficient modulus of strength, lower thermo-physical properties, etc., compared to traditional plastics.
Polyglycolic acid (PGA), also known as polyglycolide or polyglycolic acid, is the simplest linear aliphatic polyester, and has good biodegradability and biocompatibility. Among all the biodegradable polyesters at present, the gas barrier property and heat resistance are the best, and the tensile strength and flexural strength are the highest. However, the thermal decomposition temperature and the processing temperature are very close, the processing temperature range in practical application is very narrow and is between 230 ℃ and 240 ℃, which is unfavorable for processing application. In view of the unique performance and potential price advantages of the PGA, the PGA and the PBAT are blended or copolymerized and modified, and the PGA-PBAT composite material has great application potential in the field of disposable products such as heat-resistant tableware, degradable film bags, barrier packages and the like.
However, because the glycolide monomer for synthesizing the PGA is expensive, the ring-opening polymerization is difficult, the mass production is difficult to realize, and meanwhile, the PGA degradation speed is high, uncontrollable, the storage period is short, and the application is limited. And another polymer Poly Methyl Glycolate (PMG) which is the same as the repeating unit of PGA has the degradable performance and higher thermal stability, and the monomer methyl hydroxy glycolate is a byproduct of coal chemical industry, and has low cost and easy obtainment. If the PGA is replaced to carry out copolymerization modification with the PBAT, on one hand, the byproduct resource is fully utilized, and the cost is reduced; on the other hand, the hydrolysis rate and the barrier property of the PBAT are improved, and the strength and the modulus are improved. However, in the prior art, a melt blending technology is mostly adopted, a melt blending system is complex, multiple components, interfacial compatibility among the multiple components and the like are involved, fluctuation of blending physical properties is easily caused, and meanwhile, corresponding auxiliary agents are added to influence biosafety.
If methyl glycolate, terephthalic acid, adipic acid and 1, 4-butanediol are directly esterified and polycondensed to prepare the quadripolymer, the esterification temperature of PBAT is generally 180-230 ℃ and the boiling point of methyl glycolate is generally about 150 ℃, so that the four monomers are difficult to realize theoretically. Based on the above, the invention takes cheap methyl glycolate as a monomer to synthesize methyl glycolate oligomer from the design of molecular structure, and then the oligomer and PBAT prepolymer are subjected to melt polycondensation reaction to prepare poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester. The method has simple process, the synthesized quaternary copolyester has low price, can replace commercial modified PBAT, and simultaneously improves the mechanical property of the material based on the introduction of methyl glycolate, and endows the copolyester with high barrier property, thereby widening the application field.
Disclosure of Invention
The invention aims to provide a degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester with low cost and high barrier property, which is biodegradable, has better strength and toughness, can be used for preparing water-degradable products, and can be rapidly degraded in natural water environment.
The second object of the invention is to provide a method for synthesizing the degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester (PBATGA) having the chemical structural formula:
Wherein the molar content (n GA) of the structural unit derived from glycolic acid is 5-40%, and the calculation is calculated according to a nuclear magnetic spectrum chart, and the specific formula is that X=60-200; y=60-200; n=2-10; the weight average molecular weight is 50000-100000g/mol.
A method for preparing biodegradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester, comprising the steps of: poly (methyl glycolate) Oligomer (OMG)Esterified polymersUnder the action of a polycondensation catalyst, carrying out vacuum melt polycondensation to obtain the product poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester.
Further, the preparation method of the polymethyl glycolate Oligomer (OMG) comprises the following steps:
Stirring and heating methyl glycolate under the action of a catalyst in an inert (inert gas such as argon, nitrogen and the like which are commonly used in the chemical field) atmosphere to react to prepare the polymethyl glycolate Oligomer (OMG).
Specifically, the method comprises the following steps: adding methyl glycolate and a catalyst into a reactor according to the proportion, heating to 170 ℃ under the protection of N 2, reacting for 3-6 h, and waiting for the fraction not to be distilled out. Heating to 180 ℃, slowly vacuumizing to ensure that the degree of vacuum gauge is 3kPa, extracting methanol, maintaining the reaction temperature to 180+/-2 ℃, until white solid is generated on the inner wall of the flask, and stopping stirring.
Further, the preparation method of the esterified polymer comprises the following steps: under the action of an esterification catalyst, 1,4 butanediol, terephthalic acid and adipic acid are subjected to esterification polymerization reaction in inert atmosphere to obtain the following esterified polymer.
Specifically, the method comprises the following steps: weighing an esterification catalyst, 1,4 butanediol, terephthalic acid and adipic acid according to a proportion, placing the materials in a three-neck flask, heating to 200 ℃ under the protection of inert gas (such as argon and nitrogen), and stirring and reacting for 4-5 h at a stirring speed of 180r/min to obtain an esterification product, namely an esterification polymer.
Further, the melt polycondensation reaction includes the steps of:
And (3) carrying out vacuum polycondensation on OMG, a polycondensation catalyst and an esterification product for 4-5 hours at the temperature of 230 ℃ to obtain the final product poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester.
The catalyst in the preparation of the polymethyl glycolate oligomer is preferably any one or more of stannous chloride dihydrate, zinc acetate dihydrate, stannous octoate and antimonous oxide, and the dosage of the catalyst is preferably 0.01-0.1% of the mass of the methyl glycolate.
Further, in the preparation of the esterified polymer, the alkyd ratio is preferably 1.8 to 2:1 (molar ratio).
Further, in the preparation of the esterified polymer, the esterification catalyst is preferably any one or more of tetrabutyl titanate, triethyl phosphate and zinc acetate, and the catalyst dosage is preferably 0.3-1% of the theoretical esterified polymer mass.
The polycondensation catalyst in the melt polycondensation is preferably tetrabutyl titanate and/or antimony trioxide, and the catalyst dosage is preferably 0.01-0.03% of the theoretical copolyester mass. The degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester provided by the invention is used for food packaging materials, has excellent oxygen barrier property and water vapor barrier property, and has good mechanical service performance.
The invention has the advantages and positive effects that:
1. The weight average molecular weight of the copolyester of the invention ranges from 50000 to 100000g/mol. The toughness is better than that of pure PGA, the strength and the barrier property are better than those of pure PBAT, the processing property is good, the melting point is higher than 90 ℃, and the preparation method can be applied to the fields of preparation of degradable food packaging materials with good barrier property and the like and has wide application prospect.
2. According to the invention, glycolic acid with better strength and barrier property is introduced into a molecular chain of PBAT, so that novel copolyester with better comprehensive properties is obtained. The methyl glycolate comes from byproducts of coal chemical industry, so that the cost is reduced, the resources are saved, and the application prospect is wide.
3. The synthesis method is a traditional melt polycondensation method, has a simple process route, can utilize the existing common device to polymerize, and is easy for industrial continuous production.
Drawings
FIG. 1 is a synthetic route diagram of a degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester in an embodiment of the present invention;
FIG. 2 is a schematic representation of the molecular chain of PBATGA copolymers of example 1;
FIG. 3 is a schematic representation of the molecular chain of PBATGA copolymers of example 2;
FIG. 4 is a schematic representation of the molecular chain of PBATGA copolymers in example 3;
FIG. 5 is an infrared spectrum of PBATGA copolyester of example 1;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of PBATGA random copolymer in example 1;
FIG. 7 is a DSC graph of the second temperature rise of PBATGA random copolymer of example 1;
FIG. 8 is a thermogram of the PBATGA random copolymer of example 1.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
the following example provides a degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester (PBATGA) having the chemical structural formula shown below:
Wherein the molar content (n GA) of the structural unit derived from glycolic acid is 5-40%, and the calculation is calculated according to a nuclear magnetic spectrum chart, and the specific formula is that X=60-200; y=60-200; n=2-10; the weight average molecular weight is 50000-100000g/mol.
Example 1:
Adding an esterification catalyst, 0.135mol (12.17 g) of 1, 4-butanediol, 0.0375mol (6.23 g) of terephthalic acid and 0.0375mol (5.48 g) of adipic acid into a clean three-neck flask according to an alkyd ratio of 1.8:1, putting the three-neck flask with the raw materials into a salt bath pot heated to 200 ℃ in advance, introducing N 2 into a reaction system, introducing a water separator, setting up a condensation and stirring device, raising the temperature to 200-230 ℃ stepwise, maintaining the stirring rotation speed at 180r/min, removing small molecules such as water and tetrahydrofuran generated in the reaction process under the blowing of nitrogen in the esterification reaction process until the liquid output amount reaches 95% of a theoretical value, judging that the esterification reaction is finished, and obtaining transparent liquid, namely PBAT copolyester prepolymer, wherein the general esterification reaction time is 4-5 h.
To the above-obtained PBAT copolyester prepolymer, 0.35g of oligomeric polymethyl glycolate and 0.024g of antimony trioxide were added. Maintaining the temperature at 230 ℃, removing the condenser tube and the water separator, vacuumizing the system, wherein the vacuum degree is less than 30Pa, the stirring rotation speed is reduced to 160-60 r/min in a stepwise manner according to the change of the viscosity, stopping vacuumizing when the product viscosity is high or the phenomenon of pole climbing occurs, and waiting for the room temperature to collect the final product.
The melting point of the product was 125.9 ℃, mn=37943, mw=68740, pdi=1.81, elongation at break 1304%, oxygen permeability coefficient 2.049×10 -16cm3·cm/cm2 ·s·pa, calculated by nuclear magnetic resonance spectroscopy, r=0.78, indicating that the copolymer obtained is a block copolymer, schematic diagram of this copolymer in fig. 2.
Example 2
Adding an esterification catalyst, 0.135mol (12.17 g) of 1, 4-butanediol, 0.0375mol (6.23 g) of terephthalic acid and 0.0375mol (5.48 g) of adipic acid into a clean three-neck flask according to an alkyd ratio of 1.8:1, putting the three-neck flask with the raw materials into a salt bath pot heated to 200 ℃ in advance, introducing N2 into a reaction system, introducing a water knockout drum, setting up a condensation and stirring device, heating to 200-230 ℃ stepwise, maintaining the stirring rotation speed at 180r/min, removing small molecules such as water and tetrahydrofuran generated in the reaction process under the blowing of nitrogen in the esterification reaction process until the liquid output amount reaches 95% of a theoretical value, judging that the esterification reaction is finished, and obtaining transparent liquid, namely PBAT copolyester prepolymer, wherein the general esterification reaction time is 4-5 h.
To the above-obtained PBAT copolyester prepolymer, 1.58g of oligomeric polymethyl glycolate and 0.026g of antimony trioxide were added. Maintaining the temperature at 230 ℃, removing the condenser tube and the water separator, vacuumizing the system, wherein the vacuum degree is less than 30Pa, the stirring rotation speed is reduced to 160-60 r/min in a stepwise manner according to the change of the viscosity, stopping vacuumizing when the product viscosity is high or the phenomenon of pole climbing occurs, and waiting for the room temperature to collect the final product.
The melting point of the product was detected to be 109.9 ℃, mn=52059, mw= 84805, pdi=1.63, elongation at break to 752%, oxygen permeability coefficient to 6.02× -14cm3·cm/cm2 ·s·pa, and r=0.79 calculated from nuclear magnetic resonance spectroscopy, indicating that the copolymer obtained was a block copolymer, and fig. 3 is a schematic diagram of the copolymer.
Example 3
Adding an esterification catalyst, 0.135mol (12.17 g) of 1, 4-butanediol, 0.0375mol (6.23 g) of terephthalic acid and 0.0375mol (5.48 g) of adipic acid into a clean three-neck flask according to an alkyd ratio of 1.8:1, putting the three-neck flask with the raw materials into a salt bath pot heated to 200 ℃ in advance, introducing N2 into a reaction system, introducing a water knockout drum, setting up a condensation and stirring device, heating to 200-230 ℃ stepwise, maintaining the stirring rotation speed at 180r/min, removing small molecules such as water and tetrahydrofuran generated in the reaction process under the blowing of nitrogen in the esterification reaction process until the liquid output amount reaches 95% of a theoretical value, judging that the esterification reaction is finished, and obtaining transparent liquid, namely PBAT copolyester prepolymer, wherein the general esterification reaction time is 4-5 h.
To the above-obtained PBAT copolyester prepolymer, 3.15g of oligomeric polymethyl glycolate and 0.028g of antimony trioxide were added. Maintaining the temperature at 230 ℃, removing the condenser tube and the water separator, vacuumizing the system, wherein the vacuum degree is less than 30Pa, the stirring rotation speed is reduced to 160-60 r/min in a stepwise manner according to the change of the viscosity, stopping vacuumizing when the product viscosity is high or the phenomenon of pole climbing occurs, and waiting for the room temperature to collect the final product.
The melting point of the product was 92.93 ℃, mn=61847, mw=109126, pdi=1.76, elongation at break of 601%, oxygen permeability coefficient of 6.37×10 -14cm3·cm/cm2 ·s·pa, r=1.12 calculated from nuclear magnetic resonance spectroscopy, indicating that the copolymer obtained is a random copolymer, and schematic diagram of this copolymer is shown in fig. 4.
The corresponding polyesters obtained in examples 1-3 above were tested for mechanical properties, oxygen and water vapor transmission rates, and the specific test results are shown in Table 1. Wherein the tensile strength and the elongation at break are detected according to national standard GB/T1040.3-2006; the oxygen transmittance coefficient is detected according to national standard GB/T1038-2000; the water vapor transmission rate was measured according to GB/T1037-2021.
Table 1:
FIG. 5 is an infrared spectrum of PBATGA copolyester of example 1, wherein about 2961cm -1 is the stretching vibration peak of-CH 2, about 1709cm -1 is the stretching vibration peak of C=Ocarbonyl, 1410cm -1 and 1389cm -1 are the in-plane bending vibration peaks of-CH 2, and 1267cm -1、 1167cm-1、1119cm-1、1103cm-1 are both stretching vibration peaks of C-O-C bonds; 725cm -1 is the out-of-plane bending vibration peak of the C-H bond on the disubstituted benzene ring.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of PBATGA random copolymer in example 1. Delta=8.09 ppm (a) is the chemical shift of H on the benzene ring in terephthalic acid, delta=4.6 ppm to 5.0ppm (b 1 to b 5) is the chemical shift of H on the two methylene groups in glycolic acid, delta=4.36 ppm (f) to 4.43ppm (b) is the chemical shift of H on the two methylene groups in 1,4 butanediol near the carbonyl group in terephthalic acid, delta=4.08 ppm (d) to 4.16ppm (i) is the chemical shift of H on the two methylene groups in 1,4 butanediol near the carbonyl group in adipic acid, delta=2.33 ppm (j) is the chemical shift of H on the two methylene groups in adipic acid near the carbonyl group, delta=2.33 ppm (j) is the chemical shift of H on the two methylene groups in adipic acid, delta=1.97 ppm (c) is the chemical shift of H on the two methylene groups in 1,4 butanediol away from the carbonyl group in terephthalic acid, delta=1.75 ppm (H) to 1.92ppm (g) is the chemical shift of H on the two methylene groups in adipic acid and delta=1.69 ppm (j) is the chemical shift of H on the two methylene groups in adipic acid. As noted above, the product was PBATGA copolymer.
FIG. 7 is a DSC graph of the second temperature rise of PBATGA random copolymer of example 1 with a melting temperature of 109.9 ℃.
FIG. 8 is a graph of the thermogravimetric loss of PBATGA random copolymer of example 1, which has a onset of weight loss of more than 400℃and good thermal stability.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (5)
1. A degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester, characterized by:
the preparation method of the copolyester comprises the following steps:
Adding an esterification catalyst, 0.135mol of 1, 4-butanediol, 0.0375mol of terephthalic acid and 0.0375mol of adipic acid into a clean three-neck flask according to an alkyd ratio of 1.8:1, putting the three-neck flask with the raw materials into a salt bath pot heated to 200 ℃ in advance, introducing N 2 into a reaction system, introducing a water separator, setting up a condensing and stirring device, raising the temperature to 200-230 ℃ in stages, maintaining the stirring rotating speed at 180r/min, removing water and tetrahydrofuran micromolecules generated in the reaction process under the blowing of nitrogen in the esterification reaction process until the liquid output amount in the esterification reaction process reaches 95% of a theoretical value, judging that the esterification reaction is finished, obtaining transparent liquid, namely PBAT copolyester prepolymer, and performing the esterification reaction for 4-5 h;
Adding 0.35g of oligomer poly (methyl glycolate) and 0.024g of antimonous oxide into the obtained PBAT copolyester prepolymer, maintaining the temperature at 230 ℃, removing a condenser tube and a water separator, vacuumizing the system, wherein the vacuum degree is less than 30 Pa, reducing the stirring rotation speed to 160-60 r/min in stages according to the change of the viscosity during the period, stopping vacuumizing when the viscosity of the product is high or the phenomenon of pole climbing occurs, and waiting for room temperature to collect the final product.
2. The degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester of claim 1, wherein the preparation method of the polymethyl glycolate oligomer comprises: stirring and heating methyl glycolate in inert atmosphere under the action of a catalyst to react to prepare the polymethyl glycolate oligomer.
3. The degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester of claim 2, wherein in the preparation of the polymethyl glycolate oligomer, the catalyst is any one or more of stannous chloride dihydrate, zinc acetate dihydrate, stannous octoate and antimony trioxide, and the catalyst dosage is 0.01% -0.1% of the mass of the methyl glycolate.
4. The degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester of claim 1, wherein in the preparation of the esterified polymer, the esterification catalyst is any one or more of tetrabutyl titanate, triethyl phosphate and zinc acetate, and the catalyst dosage is 0.3% -1% of the theoretical esterified polymer mass.
5. Use of a degradable poly (adipic acid/butylene terephthalate-co-glycolic acid) copolyester according to claim 1, characterized in that: is used for food packaging materials.
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