CN115124702A - Degradable aromatic-aliphatic copolyester material and preparation method and application thereof - Google Patents
Degradable aromatic-aliphatic copolyester material and preparation method and application thereof Download PDFInfo
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- CN115124702A CN115124702A CN202110324976.4A CN202110324976A CN115124702A CN 115124702 A CN115124702 A CN 115124702A CN 202110324976 A CN202110324976 A CN 202110324976A CN 115124702 A CN115124702 A CN 115124702A
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000005886 esterification reaction Methods 0.000 claims abstract description 53
- 125000003118 aryl group Chemical group 0.000 claims abstract description 51
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 115
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 77
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 36
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 35
- 229910052787 antimony Inorganic materials 0.000 claims description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 19
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 16
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005022 packaging material Substances 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 11
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 11
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 description 44
- 239000004626 polylactic acid Substances 0.000 description 42
- 238000001228 spectrum Methods 0.000 description 42
- 239000000047 product Substances 0.000 description 38
- 229920001519 homopolymer Polymers 0.000 description 32
- 238000002844 melting Methods 0.000 description 26
- 230000008018 melting Effects 0.000 description 26
- 230000035484 reaction time Effects 0.000 description 19
- -1 polybutylene succinate Polymers 0.000 description 17
- 238000007334 copolymerization reaction Methods 0.000 description 16
- 238000012643 polycondensation polymerization Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000012974 tin catalyst Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000000914 diffusion-ordered spectroscopy Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 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 description 14
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 238000012544 monitoring process Methods 0.000 description 8
- 229920000954 Polyglycolide Polymers 0.000 description 7
- 229920003232 aliphatic polyester Polymers 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 229920002472 Starch Polymers 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- DGMTZMCDDBNVPU-UHFFFAOYSA-N 3,10-dioxabicyclo[10.4.0]hexadeca-1(16),12,14-triene-2,11-dione Chemical compound O=C1OCCCCCCOC(=O)C2=CC=CC=C12 DGMTZMCDDBNVPU-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical group C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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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
- C08G63/02—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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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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 discloses a degradable aromatic-aliphatic copolyester material and a preparation method and application thereof, wherein the method comprises the following steps: (1) mixing aromatic dibasic acid, dihydric alcohol, aliphatic unit and catalyst to obtain a mixture containing a ring-opening polymerization product and an esterification product; (2) and carrying out polycondensation reaction on the mixture containing the ring-opening polymerization product and the esterification product to obtain the degradable aromatic-aliphatic copolyester material. According to the method, ring-opening polymerization of an aliphatic unit, esterification reaction of aromatic dibasic acid and dibasic alcohol, and polycondensation reaction of a ring-opening polymerization product and an esterification product are combined, namely, the aromatic unit and the aliphatic unit are simultaneously introduced into a high molecular chain, so that the degradation performance of the aliphatic unit and the excellent comprehensive performance of the aromatic unit are organically combined, and the degradable polyester material with high performance and low cost is obtained, and the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of traditional plastics and the like are fundamentally solved.
Description
Technical Field
The invention belongs to the field of degradable materials, and particularly relates to a degradable aromatic-aliphatic copolyester material, and a preparation method and application thereof.
Background
With the issuance and implementation of policies such as "plastic reduction", "plastic limitation" and "plastic inhibition" in various countries in the world, the degradable polymer materials face unprecedented development opportunities and challenges, and although there are dozens of degradable plastics currently developed globally, there are not many kinds of degradable plastics that can be industrially produced, among them, mainly including chemically synthesized poly (adipic acid)/butylene terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), etc., while polymer materials such as Polycaprolactone (PCL), Polyglycolide (PGA), Polyhydroxyalkanoate (PHA) synthesized by microbial fermentation and polycarbonate (PPC), etc., although they also have very good biodegradable properties, due to their cost and performance factors, they are difficult to industrialize and popularize, and thus it is difficult to replace traditional plastics in a large scale in practical application. For example, aliphatic polyester PLA has significant disadvantages, such as hard and brittle texture, insufficient elasticity and flexibility, poor heat resistance, limited strength and modulus, etc., despite its good hardness, gloss, and good food and human safety, and therefore modification of PLA homopolymer is generally required to meet the use requirements.
Common modification means include blending modification to prepare novel polymers. For example, the natural high molecular starch-based degradable material widely used in the packaging industry at present has the advantages that the cost of the final degradable material product can be greatly reduced by blending starch in a certain proportion, but due to the compatibility problem of a blending system, the starch-based material is easy to age and become brittle, and the mechanical property and the water resistance are poor.
Therefore, the existing degradable materials need to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a degradable aromatic-aliphatic copolyester material, a preparation method and an application thereof, the method combines ring-opening polymerization of aliphatic units, esterification reaction of aromatic dibasic acid and dibasic alcohol, and polycondensation reaction of ring-opening polymerization products and esterification products, namely, simultaneously introduces aromatic units and aliphatic units into a high molecular chain, so that the degradation performance of the aliphatic units is organically combined with the excellent comprehensive performance of the aromatic units, and the degradable polyester material with high performance and low cost is obtained, thereby fundamentally solving the bottleneck problems of poor mechanical properties of the degradable polyester material, non-degradability of traditional plastics and the like.
In one aspect of the present invention, a method of preparing a degradable aromatic-aliphatic copolyester material is presented. According to an embodiment of the invention, the method comprises:
(1) mixing aromatic dibasic acid, dihydric alcohol, aliphatic unit and a catalyst, wherein under the action of the catalyst, one part of the dihydric alcohol initiates ring-opening polymerization reaction of the aliphatic unit, and the other part of the dihydric alcohol and the aromatic dibasic acid undergo esterification reaction, so as to obtain a mixture containing a ring-opening polymerization product and an esterification product;
(2) and carrying out polycondensation reaction on the mixture containing the ring-opening polymerization product and the esterification product so as to obtain the degradable aromatic-aliphatic copolyester material.
According to the method for preparing the degradable aromatic-aliphatic copolyester material, the aromatic dibasic acid, the dihydric alcohol, the aliphatic unit and the catalyst are mixed, under the action of the catalyst, one part of the dihydric alcohol initiates the ring-opening polymerization reaction of the aliphatic unit, and the other part of the dihydric alcohol and the aromatic dibasic acid generate the esterification reaction to obtain a mixture containing a ring-opening polymerization product and an esterification product, then the mixture containing the ring-opening polymerization product and the esterification product is subjected to the polycondensation reaction to obtain the degradable aromatic-aliphatic copolyester material, namely, the method combines the ring-opening polymerization of the aliphatic unit, the esterification reaction of the aromatic dibasic acid and the dihydric alcohol and the polycondensation reaction of the ring-opening polymerization product and the esterification product, namely, the aromatic unit and the aliphatic unit are simultaneously introduced into a macromolecular chain, the degradation performance of the aliphatic unit and the excellent comprehensive performance of the aromatic unit are organically combined to obtain the degradable polyester material with high performance and low cost, so that the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of the traditional plastic and the like are fundamentally solved. In addition, the preparation method has stable process and easily controlled reaction process, adopts one-pot reaction and one-time feeding, does not need to break vacuum in the reaction process and open a kettle for feeding, and avoids side reaction caused by oxygen.
In addition, the method for preparing a degradable aromatic-aliphatic copolyester material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in step (1), the aromatic dibasic acid comprises at least one of terephthalic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalic acid ester, phthalic acid ester, isophthalic acid ester, furandicarboxylic acid ester, 2, 6-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylic acid ester, preferably at least one of terephthalic acid and 2, 6-naphthalenedicarboxylic acid. Therefore, the mechanical property and the thermal property of the polyester material can be obviously improved.
In some embodiments of the invention, in step (1), the glycol comprises at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol, preferably ethylene glycol.
In some embodiments of the invention, in step (1), the aliphatic unit comprises at least one of lactic acid, glycolic acid, lactide and glycolide, preferably lactide.
In some embodiments of the present invention, in step (1), the aromatic dibasic acid and the glycol are in a molar ratio of 1: (1.1-2), preferably 1: (1.2-1.8).
In some embodiments of the present invention, in step (1), the feeding molar ratio of the aromatic dibasic acid to the aliphatic unit is (1-99): (1-99), preferably (10-90): (10-90).
In some embodiments of the present invention, in step (1), the amount of the catalyst is 1% to 5%, preferably 1% to 3%, of the total mass of all raw materials.
In some embodiments of the present invention, in step (1), the catalyst comprises an antimony-based catalyst and a tin-based catalyst.
In some embodiments of the present invention, in the step (1), the temperature of the ring-opening polymerization reaction is 180 to 220 ℃ and the time is 1 to 3 hours.
In some embodiments of the present invention, in the step (1), the temperature of the esterification reaction is 220 to 250 ℃ and the time is 1 to 32 hours.
In some embodiments of the present invention, in the step (2), the temperature of the polycondensation reaction is 260 to 270 ℃ for 1 to 3 hours.
In some embodiments of the present invention, in step (2), the degradable aromatic-aliphatic copolyester material has a viscosity of 0.5 to 0.7 dL/g. In a second aspect of the present invention, the present invention provides a degradable aromatic-aliphatic copolyester material. According to the embodiment of the invention, the degradable aromatic-aliphatic copolyester material is prepared by adopting the method. Therefore, the degradable material realizes the organic combination of the degradation performance of aliphatic polyester and the excellent comprehensive performance of aromatic polyester, has the advantages of high performance and low cost, and fundamentally solves the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of traditional plastics and the like.
In a third aspect of the present invention, a packaging material is presented. According to an embodiment of the present invention, the packaging material is prepared by using the degradable aromatic-aliphatic copolyester material. Therefore, the degradable material with the advantages of high performance and low cost is adopted to prepare the packaging material, so that the cost of the packaging material can be reduced while the performance of the packaging material is improved, and the degradable material is beneficial to industrial production and large-scale popularization and use.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing a degradable aromatic-aliphatic copolyester material according to an embodiment of the invention;
FIG. 2 is a hydrogen nuclear magnetic spectrum of the copolyester obtained in example 1;
FIG. 3 is the DOSY nuclear magnetic spectrum of the copolyester obtained in example 1;
FIG. 4 is a DSC spectrum of the copolyester obtained in example 1.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the present invention, a method of preparing a degradable aromatic-aliphatic copolyester material is presented. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing aromatic dibasic acid, dihydric alcohol, aliphatic unit and catalyst
In the step, aromatic dibasic acid, dihydric alcohol, an aliphatic unit and a catalyst are mixed, under the action of the catalyst, one part of the dihydric alcohol initiates ring-opening polymerization reaction of the aliphatic unit to obtain a ring-opening polymerization product, and the other part of the dihydric alcohol and the aromatic dibasic acid undergo esterification reaction to obtain an esterification product, so that a mixture containing the ring-opening polymerization product and the esterification product is obtained. Preferably, the aromatic dibasic acid includes but is not limited to at least one of terephthalic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalate, phthalate, isophthalate, furandicarboxylate, 2, 6-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylic acid, preferably at least one of terephthalic acid and 2, 6-naphthalenedicarboxylic acid, and the aromatic unit has a rigid benzene ring structure in a segment thereof, so that the material has excellent mechanical and thermal properties, and the aromatic dibasic acid has low material cost, cheap and easily available raw materials and is not limited by suppliers. In addition, the 2, 6-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylate have naphthalene rings with higher rigidity in molecular chains, and the naphthalene ring structure enables the material to have higher physical and mechanical properties, gas barrier property, chemical stability, heat resistance, ultraviolet resistance, radiation resistance and other properties, so that the 2, 6-naphthalenedicarboxylic acid unit is introduced into the molecular chains, the overall comprehensive performance of the copolymer is further improved, and the final material has wider application prospects. Further, the above-mentioned glycols include, but are not limited to, at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol, preferably ethylene glycol; the dihydric alcohol is used as a multifunctional monomer and a reaction solvent, can initiate ring-opening polymerization reaction, can participate in polycondensation reaction with aromatic dibasic acid, and participates in construction. The aliphatic unit includes, but is not limited to, at least one of lactic acid, glycolic acid, lactide and glycolide, preferably lactide.
Meanwhile, the molar ratio of the aromatic dibasic acid to the dihydric alcohol is 1: (1.1-2), preferably 1: (1.2-1.8). The inventor finds that if the ratio of the two is too low, the glycol is consumed along with the reaction, the reaction can be incomplete, and the final yield of the polymer is reduced; if the ratio of the two is too high, the DEG content in the product is too high, and the thermal property of the obtained product is reduced. Further, the feeding molar ratio of the aromatic dibasic acid to the aliphatic unit is (1-99): (1-99), preferably (10-90): (10-90). Meanwhile, the dosage of the catalyst is 1-5%, preferably 1-3% of the total mass of all the raw materials, and the catalyst comprises an antimony catalyst and a tin catalyst. The tin catalyst has excellent activity and product selectivity for ring opening polymerization, can greatly improve the purity of reaction products, and improve the conversion rate of aliphatic units and the insertion amount of the aliphatic units in the target copolyester; the antimony-based catalyst has excellent activity in the condensation polymerization step, and can effectively catalyze the condensation polymerization of each unit, thereby obtaining the copolyester material with high viscosity. In the present application, all the raw materials include aromatic dibasic acid, diol and aliphatic polyester, and the proportion of the antimony-based catalyst and the tin-based catalyst in the catalyst may be selected according to specific needs in the art.
Further, the temperature of the ring-opening polymerization reaction is 180-220 ℃, and the time is 1-3 h, preferably 2 h; the temperature of the esterification reaction is 220-250 ℃, and the time is 1-3 h, preferably 2 h.
S200: subjecting a mixture containing a ring-opening polymerization product and an esterification product to a polycondensation reaction
In the step, the reaction temperature is slowly increased, and the obtained mixture containing the ring-opening polymerization product and the esterification product is subjected to polycondensation reaction at 260-270 ℃ for 1-3 h, preferably 2h, so as to obtain the degradable aromatic-aliphatic copolyester material with the viscosity of 0.5-0.7 dL/g. The inventor finds that the polymerization reaction time has a great influence on the viscosity of the final product, and the reaction is incomplete when the reaction time is short, so that the yield of the polymer is low and the viscosity of the polymer is insufficient; longer polymerization times can lead to degradation of the aliphatic unit segments, also can substantially reduce the viscosity of the final product, and can darken the color.
Specifically, the aromatic dibasic acid contains a benzene ring rigid structure, so that a final product can be provided with higher glass transition temperature and use temperature, excellent mechanical properties can be provided for materials, and the copolyester is provided with higher tensile strength; the dihydric alcohol and the aliphatic unit enhance the flexibility of a polymer chain, and are determined by balancing poor solubility, poor processability and the like caused by excessive aromatic units, and the introduction of the aliphatic polyester unit can inhibit crystallization, thereby obtaining a copolyester material with better transparency. More importantly, with the increase of the content of the aliphatic polyester, the final material can have certain degradation performance, and the requirement of environmental protection is met, so that the organic combination of aromatic dibasic acid, dihydric alcohol and aliphatic units is realized, the thermal performance, the processing performance, the mechanical performance and the degradation performance of the copolyester are synergistically improved, and the performance of the final material can be freely switched and regulated by regulating the proportion of each unit and the distribution condition in a high molecular chain, so that a wider application scene is met. Meanwhile, the introduction of the lactic acid unit can reduce the glass transition temperature of the copolymer, and the application range of the copolyester is limited, so that the naphthalene dicarboxylic acid unit with higher glass transition temperature is innovatively introduced while the lactic acid unit is adopted, so that the influence of thermal property reduction brought by lactic acid is offset, and the copolyester material with more excellent and balanced comprehensive properties is prepared.
Taking terephthalic acid, ethylene glycol and lactide as an example, the reaction equation is as follows:
in a second aspect of the present invention, a degradable aromatic-aliphatic copolyester material is provided. According to the embodiment of the invention, the degradable aromatic-aliphatic copolyester material is prepared by adopting the method. Therefore, the degradable material realizes the organic combination of the degradation performance of aliphatic polyester and the excellent comprehensive performance of aromatic polyester, has the advantages of high performance and low cost, and fundamentally solves the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of traditional plastics and the like. It should be noted that the features and advantages described above for the method for preparing the degradable aromatic-aliphatic copolyester material are also applicable to the degradable aromatic-aliphatic copolyester material, and are not described herein again.
In a third aspect of the present invention, a packaging material is presented. According to an embodiment of the present invention, the packaging material is prepared by using the degradable aromatic-aliphatic copolyester material. Therefore, the degradable material with the advantages of high performance and low cost is adopted to prepare the packaging material, so that the cost of the packaging material can be reduced while the performance of the packaging material is improved, and the degradable material is beneficial to industrial production and large-scale popularization and use. Specifically, the packaging material is a disposable food packaging bag, a disposable medical packaging bag and the like. It should be noted that the features and advantages described above for the degradable aromatic-aliphatic copolyester material and the preparation method thereof are also applicable to the packaging material, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
At room temperature, 2180g of lactide monomer, 4900g of terephthalic acid (PTA), 81.5g of isophthalic acid (IPA), 2460g of Ethylene Glycol (EG) and a catalyst (128 g of tin catalyst stannous octoate and antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 180 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 220 ℃, esterification reaction is continuously carried out under a pressurized condition for 2 hours, the esterification reaction water yield is monitored in the reaction process, after the reaction is finished, the temperature is increased to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET and PLA, the molar ratio of aromatic to aliphatic is about 66: 34; the PET unit and the PLA unit have equal diffusion coefficients according to the DOSY nuclear magnetic spectrum of the obtained aromatic-aliphatic copolyester, the success of copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; meanwhile, the DSC spectrogram of the obtained copolyester shows that the copolyester does not contain a melting point, is an amorphous polymer and indicates that the two components are in a copolymerization state but not in a blending state.
Example 2
At room temperature, fully stirring 1600g of lactide monomer, 5410g of terephthalic acid (PTA), 89.6g of isophthalic acid (IPA), 2710g of Ethylene Glycol (EG), and catalysts (tin catalyst stannous octoate + antimony catalyst antimony acetate 128g), uniformly mixing, adding the mixture into a 20L reaction kettle, heating to 200 ℃ for reaction for 2 hours, then slowly heating the reaction temperature to 220 ℃, continuously carrying out esterification reaction under a pressurization condition for 2 hours, monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, heating to 260 ℃ for condensation polymerization reaction, monitoring the torque change in the polymerization process, after the torque is stable, finishing the reaction, discharging, cutting into particles, drying, and testing results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET and PLA, the molar ratio of aromatic to aliphatic is about 71: 29; the PET unit and the PLA unit have equal diffusion coefficients according to the DOSY nuclear magnetic spectrum of the obtained aromatic-aliphatic copolyester, the success of copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; meanwhile, the DSC spectrogram of the obtained copolyester shows that the copolyester does not contain a melting point, is an amorphous polymer and indicates that the two components are in a copolymerization state but not in a blending state.
Example 3
At room temperature, 1100g of lactide monomer, 5900g of terephthalic acid (PTA), 98g of isophthalic acid (IPA), 2960g of Ethylene Glycol (EG) and 128g of catalyst (tin catalyst stannous octoate + antimony catalyst antimony acetate), which are totally stirred and uniformly mixed, are added into a 20L reaction kettle, the temperature is increased to 200 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 220 ℃, esterification reaction is continuously carried out under a pressurized condition for 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET and PLA, the molar ratio of aromatic to aliphatic is about 79: 21; the obtained DOSY nuclear magnetic spectrum of the aromatic-aliphatic copolyester can show that a PET unit and a PLA unit have equal diffusion coefficients, the successful copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectra of the obtained PET and PLA copolyesters, the copolyester has only one melting point of about 223 ℃ and is between the melting points of the PET homopolymer and the PLA homopolymer, indicating that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 137 ℃.
Example 4
At room temperature, 690g of lactide monomer, 6400g of terephthalic acid (PTA), 105g of isophthalic acid (IPA), 3200g of Ethylene Glycol (EG) and 128g of catalyst (tin catalyst stannous octoate + antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 200 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 220 ℃, esterification reaction is continuously carried out under a pressurization condition, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is completed, the temperature is increased to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stable, the reaction is completed, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET and PLA, the molar ratio of aromatic to aliphatic is about 81: 19; the obtained DOSY nuclear magnetic spectrum of the aromatic-aliphatic copolyester can show that a PET unit and a PLA unit have equal diffusion coefficients, the successful copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectra of the obtained PET and PLA copolyesters, the copolyester has only one melting point of about 235 ℃ and is between the melting points of the PET homopolymer and the PLA homopolymer, indicating that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 142 ℃.
Example 5
At room temperature, 330g of lactide monomer, 6900g of terephthalic acid (PTA), 114g of isophthalic acid (IPA), 3460g of Ethylene Glycol (EG) and 128g of catalyst (tin catalyst stannous octoate + antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 200 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 220 ℃, esterification reaction is continuously carried out under a pressurization condition for 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET and PLA, the molar ratio of aromatic to aliphatic is about 92: 8; the PET unit and the PLA unit have equal diffusion coefficients according to the DOSY nuclear magnetic spectrum of the obtained aromatic-aliphatic copolyester, the success of copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectra of the obtained PET and PLA copolyesters, the copolyester has only one melting point of about 247 ℃ and is between the melting points of the PET homopolymer and the PLA homopolymer, indicating that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 150 ℃.
Example 6
At room temperature, 330g of lactide monomer, 6500g of terephthalic acid (PTA), 790g of 2, 6-naphthalenedicarboxylic acid (NDA), 114g of isophthalic acid (IPA), 3460g of Ethylene Glycol (EG) and 128g of catalyst (tin catalyst stannous octoate + antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 200 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 220 ℃, the esterification reaction is continuously carried out under the pressurized condition, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, the torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, the discharging, the grain cutting and the drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET, PEN and PLA, the molar ratio of aromatic to aliphatic is about 91: 9; the nuclear magnetic spectrum of the DOSY of the obtained aromatic-aliphatic copolyester can show that PET units, PEN units and PLA units have equal diffusion coefficients, the successful copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectra of the obtained PET and PLA copolyesters, the copolyester has only one melting point of about 248 ℃ and is between the melting points of the PET homopolymer and the PLA homopolymer, indicating that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 183 ℃.
Example 7
At room temperature, 330g of lactide monomer, 6100g of terephthalic acid (PTA), 1570g of 2, 6-Naphthalene Dicarboxylic Acid (NDA), 114g of isophthalic acid (IPA), 3460g of Ethylene Glycol (EG) and a catalyst (128 g of tin catalyst stannous octoate and antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is raised to 200 ℃ for reaction for 2 hours, then the reaction temperature is slowly raised to 220 ℃, the esterification reaction is continuously carried out under a pressurized condition, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 260 ℃ for condensation polymerization reaction, the reaction time is 2 hours, the torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, the discharging, the grain cutting and the drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET/PLA/PEN, the molar ratio of aromatic to aliphatic is about 89: 11; the obtained DOSY nuclear magnetic spectrum of the aromatic-aliphatic copolyester can show that PET/PLA/PEN units have equal diffusion coefficients, the successful copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectrum of the obtained PET/PLA/PEN copolyester, which has only one melting point of about 251 ℃ and is between the melting points of the PET homopolymer and the PLA homopolymer, it is shown that the two components are in a copolymerized state rather than in a blended state, and the crystallization temperature of the copolymer is about 142 ℃.
Example 8
At room temperature, fully stirring and uniformly mixing 600g of lactic acid monomer, 114g of phthalic acid, 5800g of furandicarboxylic acid, 4200g of propylene glycol and a catalyst (128 g of tin catalyst stannous octoate and antimony catalyst antimony acetate), adding the mixture into a 20L reaction kettle, heating to 200 ℃ for reaction for 2 hours, then slowly heating the reaction temperature to 220 ℃, continuing esterification reaction under a pressurized condition for 2 hours, monitoring the water yield of the esterification reaction in the reaction process, heating to 270 ℃ after the reaction is completed, carrying out condensation polymerization reaction for 2 hours, monitoring the torque change in the polymerization process, finishing the reaction after the torque is stable, discharging, granulating and drying, wherein the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of polyfurandicarboxylic acid and polylactide, the molar ratio of aromatic to aliphatic is about 85: 15; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that polyfurandicarboxylic acid and polylactide units have equal diffusion coefficients, the successful copolymerization of the two units is verified, and the obtained product does not contain any homopolymer; the copolyester has only one melting point of about 240 ℃ and is between the melting points of the polyfurandicarboxylic acid and polylactide homopolymers, indicating that the two components are in a copolymerized state rather than in a blended state, and that the crystallization temperature of the copolymer is about 133 ℃.
Example 9
660g of lactic acid monomer, 6300g of terephthalic acid, 900g of 2, 6-naphthalenedicarboxylic acid, 5100g of butanediol and 150g of catalyst (tin catalyst stannous octoate and antimony catalyst antimony acetate) are fully stirred and uniformly mixed at room temperature, the mixture is added into a 20L reaction kettle, the temperature is increased to 210 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 230 ℃, esterification reaction is continuously carried out under the condition of pressurization, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 275 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester of PET/PEN/PLA, the molar ratio of aromatic to aliphatic is about 86: 14; the nuclear magnetic spectrum of the DOSY of the obtained aromatic-aliphatic copolyester can show that PET/PEN/PLA units have equal diffusion coefficients, the successful copolymerization of the two units is proved, and the obtained product does not contain any homopolymer; from the DSC spectrum of the obtained PET/PEN/PLA copolyester, which has only one melting point of about 258 ℃ and is between the melting points of the PET/PEN/PLA homopolymers, it is indicated that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 156 ℃.
Example 10
At room temperature, 560g of glycolic acid monomer, 6400g of terephthalate, 460g of furan dicarboxylate, 5600g of pentanediol and 180g of catalyst (tin catalyst stannous octoate + antimony catalyst antimony acetate) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 220 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 250 ℃, esterification reaction is continuously carried out under the condition of pressurization, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 275 ℃ for condensation polymerization reaction, the reaction time is 2 hours, torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, the discharging, the grain cutting and the drying are carried out, and the test results are shown in Table 1. According to the hydrogen nuclear magnetic spectrum of the copolyester of the polyfurandioctyl phthalate/PGA, the molar ratio of aromatic to aliphatic is about 90: 10; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that the polyfurandioctyl phthalate/PGA unit has equal diffusion coefficient, the successful copolymerization of the two units is verified, and the obtained product does not contain any homopolymer; from the DSC spectrum of the obtained pentosan-phthalate/PGA copolyester, the copolyester has only one melting point of about 250 ℃ and is between the melting points of the pentosan-phthalate/PGA homopolymer, which indicates that the two components are in a copolymerized state rather than a blended state, and the crystallization temperature of the copolymer is about 120 ℃.
Example 11
At room temperature, 350g of glycolide, 720g of phthalate, 6100g of furan dicarboxylate, 6200g of hexanediol and a catalyst (tin catalyst stannous octoate and antimony catalyst antimony acetate are 200g in total) are fully stirred and uniformly mixed, the mixture is added into a 20L reaction kettle, the temperature is increased to 220 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 250 ℃, the esterification reaction is continued under the condition of pressurization, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 270 ℃ for condensation polymerization reaction, the reaction time is 2 hours, the torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, the discharging, the grain cutting and the drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the copolyester of polyhexamethylene phthalate and PGA, the molar ratio of aromatic to aliphatic is about 89: 11; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that the units of the poly (hexamethylene phthalate) and the PGA have equal diffusion coefficients, the successful copolymerization of the two units is verified, and the obtained product does not contain any homopolymer; from the DSC spectra of the obtained polyhexamethylene phthalate and PGA copolyester, which has only one melting point of about 261 ℃ and is between the melting points of the polyhexamethylene phthalate and PGA homopolymer, it is shown that the two components are in a copolymerized state rather than in a blended state, and the crystallization temperature of the copolymer is about 110 ℃.
Example 12
At room temperature, fully stirring and uniformly mixing 800g of lactide, 5600g of isophthalate, 780g of 2, 6-naphthalenedicarboxylic acid, 3450g of ethylene glycol and a catalyst (220 g of stannous octoate serving as a tin catalyst and antimony acetate serving as an antimony catalyst), adding the mixture into a 20L reaction kettle, heating to 200 ℃ for reaction for 2 hours, slowly heating the reaction temperature to 240 ℃, continuously carrying out esterification reaction under a pressurized condition for 2 hours, monitoring the water yield of the esterification reaction in the reaction process, heating to 270 ℃ after the reaction is finished, carrying out condensation polymerization reaction for 2 hours, monitoring torque change in the polymerization process, finishing the reaction after the torque is stable, discharging, granulating and drying, wherein the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the copolyester of the polyethylene isophthalate and the PLA, the molar ratio of aromatic to aliphatic is about 85: 15; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that polyethylene isophthalate and PLA units have equal diffusion coefficients, the successful copolymerization of the two units is verified, and the obtained product does not contain any homopolymer; from the DSC spectra of the resulting polyethylene isophthalate and PLA copolyesters, which have only one melting point of about 255 ℃ and between the melting points of the polyethylene isophthalate and PLA homopolymers, it is stated that the two components are in the copolymerized state rather than in the blended state, and that the crystallization temperature of the copolymer is about 125 ℃.
Example 13
At room temperature, fully stirring 650g of lactide, 1200g of furan dicarboxylate, 180g of 2, 6-naphthalenedicarboxylic acid, 4200g of ethylene glycol, 3450g of ethylene glycol and a catalyst (180 g of tin catalyst stannous octoate and antimony catalyst antimony acetate), uniformly mixing, adding the mixture into a 20L reaction kettle, heating to 220 ℃ for reaction for 2 hours, then slowly heating the reaction temperature to 250 ℃, continuing esterification reaction under a pressurized condition for 2 hours, monitoring the water yield of the esterification reaction in the reaction process, after the reaction is completed, heating to 275 ℃ for condensation polymerization reaction for 2 hours, monitoring the torque change in the polymerization process, after the torque is stable, completing the reaction, discharging, granulating, drying, and testing results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained PEN/PEF/PLA copolyester, the molar ratio of aromatic to aliphatic is about 81: 19; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that PEN/PEF/PLA units have equal diffusion coefficients, the successful copolymerization of the two units is verified, and the obtained product does not contain any homopolymer; from the DSC spectrum of the obtained PEN/PEF/PLA copolyester, which has only one melting point of about 260 ℃ and is between the melting points of the PEN/PEF/PLA homopolymer, it is indicated that the two components are in the copolymerized state rather than in the blended state, and the crystallization temperature of the copolymer is about 130 ℃.
Example 14
At room temperature, 480g of lactide, 6400g of phthalic acid, 780g of 2, 6-naphthalenedicarboxylate, 4800g of butanediol and a catalyst (220 g of stannous octoate serving as a tin catalyst and antimony acetate serving as an antimony catalyst) are fully stirred and mixed uniformly, the mixture is added into a 20L reaction kettle, the temperature is increased to 220 ℃ for reaction for 2 hours, then the reaction temperature is slowly increased to 250 ℃, the esterification reaction is continuously carried out under the pressurization condition, the reaction time is 2 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is increased to 270 ℃ for condensation polymerization reaction, the reaction time is 2 hours, the torque change is monitored in the polymerization process, after the torque is stabilized, the reaction is finished, the discharging, the grain cutting and the drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained polybutylene phthalate/PLA/PEN copolyester, the molar ratio of aromatic to aliphatic is about 91: 9; the obtained aromatic-aliphatic copolyester DOSY nuclear magnetic spectrum shows that polybutylene terephthalate/PLA/PEN units have equal diffusion coefficients, and the fact that the copolymerization of the two units is successful is verified, and the obtained product does not contain any homopolymer; from the DSC spectrum of the obtained polybutylene phthalate/PLA/PEN copolyester, the copolyester has only one melting point of about 257 ℃ and is between the melting points of the polybutylene phthalate/PLA/PEN homopolymers, which indicates that the two components are in a copolymerized state rather than a blended state, and the crystallization temperature of the copolymer is about 99 ℃.
TABLE 1 Property parameters of the copolyesters obtained in examples 1 to 14
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (14)
1. A method of preparing a degradable aromatic-aliphatic copolyester material, comprising:
(1) mixing aromatic dibasic acid, dihydric alcohol, aliphatic unit and a catalyst, wherein under the action of the catalyst, one part of the dihydric alcohol initiates ring-opening polymerization reaction of the aliphatic unit, and the other part of the dihydric alcohol and the aromatic dibasic acid undergo esterification reaction, so as to obtain a mixture containing a ring-opening polymerization product and an esterification product;
(2) and carrying out polycondensation reaction on the mixture containing the ring-opening polymerization product and the esterification product so as to obtain the degradable aromatic-aliphatic copolyester material.
2. The method according to claim 1, wherein in the step (1), the aromatic dibasic acid comprises at least one of terephthalic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalate, phthalate, isophthalate, furandicarboxylate, 2, 6-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylate.
3. The method according to claim 1, wherein in step (1), the diol comprises at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
4. The method of claim 1, wherein in step (1), the aliphatic unit comprises at least one of lactic acid, glycolic acid, lactide, and glycolide.
5. The method according to any one of claims 1 to 4, wherein in step (1), the molar ratio of the aromatic dibasic acid to the glycol is 1: (1.1-2).
6. The method according to claim 1, wherein in the step (1), the feeding molar ratio of the aromatic dibasic acid to the aliphatic unit is (1-99): (1-99).
7. The method according to claim 1, wherein in the step (1), the amount of the catalyst is 1 to 5% of the total mass of all the raw materials.
8. The method according to claim 1 or 7, wherein in step (1), the catalyst comprises an antimony-based catalyst and a tin-based catalyst.
9. The method according to claim 1, wherein in the step (1), the temperature of the ring-opening polymerization reaction is 180 to 220 ℃ and the time is 1 to 3 hours.
10. The method according to claim 1, wherein in the step (1), the temperature of the esterification reaction is 220-250 ℃ and the time is 1-3 h.
11. The method according to claim 1, wherein in the step (2), the temperature of the polycondensation reaction is 260 to 270 ℃ and the time is 1 to 3 hours.
12. The method according to claim 1, wherein in step (2), the degradable aromatic-aliphatic copolyester material has a viscosity of 0.5 to 0.7 dL/g.
13. A degradable aromatic-aliphatic copolyester material, wherein the degradable aromatic-aliphatic copolyester material is prepared by the method of any one of claims 1 to 12.
14. A packaging material prepared from the degradable aromatic-aliphatic copolyester material of claim 13.
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