CN102477149A - Preparation method of biodegradable aliphatic-aromatic copolyester - Google Patents
Preparation method of biodegradable aliphatic-aromatic copolyester Download PDFInfo
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- CN102477149A CN102477149A CN2010105646341A CN201010564634A CN102477149A CN 102477149 A CN102477149 A CN 102477149A CN 2010105646341 A CN2010105646341 A CN 2010105646341A CN 201010564634 A CN201010564634 A CN 201010564634A CN 102477149 A CN102477149 A CN 102477149A
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Abstract
The invention relates to a preparation method of a biodegradable aliphatic-aromatic copolyester, comprising the following steps of: a) carrying out polymerization between aliphatic dibasic acid, ester, acid anhydride or their mixture and dihydric alcohol to obtain an aliphatic polyester with a certain molecular weight, adding aromatic diacid, ester, acid anhydride or their mixture into dihydric alcohol for ester interchange or esterification, and carrying out vacuum-pumping for copolymerization to obtain the biodegradable aliphatic-aromatic copolyester; or b) carrying out copolymerization between aromatic diacid, ester, acid anhydride or their mixture and dihydric alcohol to obtain the aromatic polyester with a certain molecular weight; adding aliphatic dibasic acid, ester, acid anhydride or their mixture into dihydric alcohol for ester interchange or esterification, and carrying out vacuum-pumping for copolymerization to obtain the biodegradable aliphatic-aromatic copolyester. The product prepared by the method provided by the invention can be used in biodegradable molded products and for a purpose of mixing it with starch.
Description
Technical field
The invention belongs to field of material preparation; Be specifically related to a kind of preparation method of biodegradable aliphatic-aromatic copolyester; Degradable aliphatic-aromatic copolyester by this method preparation has excellent performances such as mechanics, calorifics and thermodynamics, can be used for preparing products such as film, spinning, sheet material, printing ink.
Background technology
Since the middle of last century, along with the continuous progress and the development of macromolecule synthesising technology and synthesis device, large-scale development has appearred in the synthetic polyester.Wherein, polyethyleneterephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) all successively are developed out, and successful realization industrialization.These three kinds of polyester performance complements cut both ways, and are active in industrial circles such as light industry, machinery, electronics, food product pack.
The widespread use of these polyphosphazene polymer ester materials has greatly made things convenient for people's productive life, yet along with the new and old replacement of product and the upgrading of regenerating, has produced a large amount of waste plastics simultaneously.This type of aromatic polyester generally is very anti-biodegradable (J.E.Potts in " Kirk-Othmer Encyclopedia of Chemical Technology "; Suppl.Vol, Wiley-Interscience, New York; 1984; Pp:626～668), can not change in underground 200 years even be embedded in, therefore the accumulation of increasing high molecular waste material develops into bioenvironmental substantial pollution gradually.The waste plastic that is poured in the ocean works the mischief to fish stock and boats and ships shipping, is embedded in subterranean waste plastic and hinders rain leakage and farmland soil conservation.Along with social development and scientific-technical progress; Under people's megatrend that protection is more and more paid attention to living environment; Basically do not influencing under the prerequisite of the daily productive life of people, macromolecular material is being carried out biodegradable modification processing become the important topic that needs urgent solution in the current polymer industrial development.
Biological degradation is meant the microbiological degradation material that nature exists, and can not cause negative impact to environment.Biodegradable plastic is meant one type of plastics that under nature microorganism such as bacterium, mould and algae effect, can resolve into micromolecular compound.Advantages such as wherein, aliphatic polyester is present one type of maximum Biodegradable high-molecular plastics of research, and its good biocompatibility, polymkeric substance and degraded product be nontoxic in addition also make it receive publicity day by day.Yet the mechanical property that this polyester is relatively poor, lower fusing point and second-order transition temperature (be lower than respectively usually 65 ℃ with-30 ℃) are difficult to satisfy in the practical application the requirement of each side such as material property, only are used in the only a few occasion.For example, the physical aspect of a lot of aliphatic polyesters is a heavy-gravity liquid under the room temperature, it is generally acknowledged that this type of aliphatic polyester is otiose.The raw materials cost height also becomes its major obstacle that further develops of restriction in addition.
Give full play to the biological degradability of aliphatic polyester and realize large-scale application, it is low just must to resolve its fusing point, the problem of poor mechanical property, and the researcher of various countries has been done a lot of research work its calorifics and mechanical property has been carried out modification.Wherein, Relatively successful example is that aliphatic polyester and aromatic polyester are carried out copolymerization; This fat/the aromatic copolyesters that obtains has thus combined the biodegradable and the excellent machinery and the processing characteristics of aromatic polyester of aliphatic polyester, therefore in biodegradable field, shows one's talent.The at present this biodegradable fat/aromatic copolyester industrialization for preparing by di-carboxylic acid and divalent alcohol and commercially available; In the copolyesters existence of aromatic units make that polymkeric substance has can actual fusing point, mechanical strength and the crystallizing power that uses; And aliphatic units makes copolyesters have the favorable biological degradability ability, reaches the requirement of getting along with environmental friendliness.
Although this copolyesters is commercially available at present; Yet its preparation process all be directly with aromatic acid/ester, aliphatic dibasic acid/ester and divalent alcohol monomer in the direct random copolymerization of synthesis phase; Perhaps after the esterification/transesterify of aromatic acid/ester and aliphatic dibasic acid/ester and divalent alcohol difference, with esterification/ester exchange offspring mixing carrying out random copolymerization.BASF patent 95196874 discloses the preparation process of its product E coflex: with hexanodioic acid and 1; 4-butyleneglycol, terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate and 1; After the esterification/transesterify of 4-butyleneglycol difference, mix hexanodioic acid 21,4-butanediol ester and terephthalic acid 21; The 4-butanediol ester vacuumizes the decompression copolymerization then and obtains random hexanodioic acid-terephthalic acid copolyesters.The polymkeric substance of this kind method preparation has constant aliphatic/aromatic unit ratio, and the peculiar fusing point that this molecular structure determined, mechanical strength etc., and this possesses stable machining and use properties is favourable for polymkeric substance is follow-up.
Though this preparation method when having guaranteed stable machining and use properties, has hindered the later stage to its modification in the molecular structure aspect.In case synthetic the completion, following process is just just carried out simple blend with other material, and the change degree of its performance is had significant limitation, is difficult to satisfy the requirement of some specific occasion.
In addition, because after the Decomposition of nature sunshine, differentiation and mikrobe, mechanical properties such as intensity reduce greatly, this is mainly because polyester molecule chain hydrolytic cleavage causes decrease in molecular weight to cause through the polyester plastics that uses.These plastics recyclings do not reach original request for utilization again, and therefore abandoning is the treatment process that present this plastics the most often use, and has caused very serious environmental problem.Though can further improve the molecular weight and the mechanical property of polyester plastics through following process such as chain extensions; But present spendable most of chainextender all is deleterious; Suitable for mass production not; Polymericular weight behind the chain extension and mechanical property still are lower than the polyester plastics before using in addition, and these following process can make that also product cost further raises simultaneously, and therefore this method can not finely address this problem.If this type of polyester plastics can be used in the polyester building-up process of next time, not only can reduce the harm of these non-degradable plastics even degradable plastics, and can a feasible terms of settlement be provided for the synthetic high raw materials cost of polyester to environment.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of biodegradable aliphatic-aromatic copolyester.At first, this preparation method can regulate aliphatics unit and the unitary ratio of aromatic series in the aliphatic-aromatic copolyester easily, and this is that the polymkeric substance that obtains having required specified property provides a kind of method very easily.Secondly; The present invention can utilize existing aliphatics or aromatic polyester finished product; Prepare biodegradable aliphatic-aromatic copolyester, extremely important actual application value is arranged for aspects such as the production cost that reduces this kind copolyesters, raising polyester plastics recovery utilization rates.
For achieving the above object, the present invention adopts following technical scheme:
The invention provides a kind of preparation method of biodegradable aliphatic-aromatic copolyester, may further comprise the steps:
Polymkeric substance d and a monomer or polymkeric substance e and b monomer are joined in the flask or reaction kettle that whipping appts and condensing works are housed with c monomer and catalyzer Cat3 together according to a certain percentage; Vacuumize, inflated with nitrogen removes the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Control reaction temperature is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; (the Theoretical Calculation amount is the twice of the molar weight of monomer a or b)
Add catalyzer Cat4, under 240～280 ℃, vacuumize (＜500Pa) stir 1～6h, stopped reaction;
Wherein: monomer a is selected from one or more the mixture in aromatic acid, ester or the acid anhydrides; Monomer b is selected from one or more the mixture in aliphatic dibasic acid, ester or the acid anhydrides; Monomer c is selected from one or more the mixture in aliphatic dihydroxy alcohol or the alicyclic divalent alcohol; Polymkeric substance d is selected from one or more the mixture in aliphatic polyester or the aromatic-aliphatic copolyester, and wherein the aliphatic poly ester units accounts for more than 50% of total amount in the copolyesters; Polymkeric substance e is selected from one or more the mixture in aromatic polyester or the aromatic-aliphatic copolyester, and wherein the aromatic polyester unit accounts for more than 50% of total amount in the copolyesters;
The mol ratio of diprotic acid unit and monomer a is 90: 10～0: 100 among the polymkeric substance d; The mol ratio of monomer a and monomer c is 1: 12～1: 3; The mol ratio of diprotic acid unit and monomer b is 90: 10～0: 100 among the polymkeric substance e; The mol ratio of monomer b and monomer c is 1: 12～1: 3; The weight fraction that catalyzer Cat3, Cat4 account for reactive component a, b and c is 0.001%～0.5%, preferred 0.005%～0.3%.
Wherein:
Described catalyzer Cat3, Cat4 are for transesterify and/or esterification being had the conventional catalyst of katalysis, like the metallic compound based on following element: Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li and Ga.
Described aromatic acid is selected from one or more the mixture in terephthalic acid, m-phthalic acid, phthalic acid or the naphthalic acid; Preferred terephthalic acid.
Described aromatic dicarboxylic ester is selected from DMT. Dimethyl p-benzenedicarboxylate; The terephthalic acid diethyl ester; Terephthalic acid di ester; Terephthalic acid diisobutyl ester; Terephthalic acid two n-pentyl esters; Terephthalic acid di neo-pentyl ester; Terephthalic acid di-n-hexyl ester; Dimethyl isophthalate; The m-phthalic acid diethyl ester; M-phthalic acid di ester; M-phthalic acid diisobutyl ester; M-phthalic acid two n-pentyl esters; M-phthalic acid di neo-pentyl ester; M-phthalic acid di-n-hexyl ester; Dimethyl phthalate; The phthalic acid diethyl ester; Phthalic acid di ester; O-benzene butyl phthalate ester; Phthalic acid two n-pentyl esters; Phthalic acid di neo-pentyl ester; Phthalic acid di-n-hexyl ester; Naphthalene diformic acid dimethyl ester; The naphthalic acid diethyl ester; Naphthalic acid di ester; Naphthalic acid diisobutyl ester; Naphthalic acid two n-pentyl esters; The mixture of one or more in naphthalic acid di neo-pentyl ester or the naphthalic acid di-n-hexyl ester; Preferred DMT. Dimethyl p-benzenedicarboxylate, dimethyl isophthalate, dimethyl phthalate or naphthalene rutgers.
Described aromatic dicarboxylic anhydride is selected from one or more the mixture in terephthalic anhydride, Tetra hydro Phthalic anhydride or the isophthalic anhydride; Preferred terephthalic anhydride.
Described aliphatic dibasic acid is selected from C
2～C
15Straight chain aliphatic dibasic acid or C
5～C
10The alicyclic diprotic acid of ring-type; Further preferred oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1; The mixture of one or more in 2-cyclohexane cyclohexanedimethanodibasic or the 1,4 cyclohexanedicarboxylic acid; The more preferably mixture of one or more in hexanodioic acid, sebacic acid or the Succinic Acid.
Described binary aliphatic ester is selected from aliphatic dibasic acid C
1-C
6Alkyl ester; The mixture of one or more in preferred dimethyl adipate, dimethyl sebacate or the methyl-succinate.
Described binary aliphatic acid anhydrides is selected from one or more the mixture in oxalic acid acid anhydride, Succinic anhydried or the adipic anhydride; Preferred Succinic anhydried.Described aliphatic dihydroxy alcohol is selected from C
2～C
13Alkanediol; Further preferred terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1,4-butyleneglycol, 1; 5-pentanediol, NSC 6366,1,6-pinakon, 1,7-heptanediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1; 12-dodecanediol, 1,13-tridecane glycol or 2-methyl isophthalic acid, the mixture of one or more in the ammediol; More preferably 1,4-butyleneglycol or terepthaloyl moietie.
Described alicyclic divalent alcohol is selected from C
5～C
10The cycloalkanes glycol; Further be selected from ring pentanediol, 1,4-cyclohexanediol, 1, the mixture of one or more in 2-cyclohexanedimethanol or the 1,4 cyclohexane dimethanol.
Described aliphatic polyester is selected from the polyglycerol fatty acid ester by linear diprotic acid and linear diols preparation; Preferably gather hexanodioic acid fourth diester, polyhexamethylene adipate, gather one or more the mixture in butylene sebacate or the poly-succinic fourth diester.
Described aromatic polyester is selected from the poly aromatic acid esters by terephthalic acid and linear diols preparation; The mixture of one or more in preferred polybutylene terephthalate, polyethyleneterephthalate or the polytrimethylene terephthalate.
Described aromatic-aliphatic copolyester is selected from by one or more the mixture in the poly aromatic acid-lipid acid copolyesters of terephthalic acid or linear diprotic acid and linear diols preparation; The mixture of one or more in preferred poly terephthalic acid-hexanodioic acid fourth diester, poly terephthalic acid-butylene sebacate or the poly terephthalic acid-Succinic Acid fourth diester.
Described catalyst component Cat3 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, acetate or the toluene-4-sulfonic acid.
Described catalyst component Cat4 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, tin compound or the antimony compounds.
Described polymkeric substance d is selected from and is purchased, reclaims or prepared by following method; May further comprise the steps: b, two kinds of monomers of c and catalyzer Cat1 are joined in the flask or reaction kettle that whipping appts and condensing works are housed according to a certain percentage; Vacuumize then, inflated with nitrogen to be to remove the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Temperature of reaction is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; (the Theoretical Calculation amount is the twice of the molar weight of monomer b) adds catalyzer Cat2, under 240～280 ℃, vacuumize (＜500Pa) stir 1～6h, stop heating, obtain polymkeric substance d;
Wherein: the mol ratio of monomer b and monomer c is 1: 12～1: 3; The weight fraction that catalyzer Cat1, Cat2 account for reactive component b and c is 0.001%～0.5%, preferred 0.005%～0.3%.Described catalyzer Cat1, Cat2 are for transesterify and/or esterification being had the conventional catalyst of katalysis, like the metallic compound based on following element: Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li and Ga.
Described polymkeric substance e is selected from and is purchased, reclaims or prepared by following method, may further comprise the steps:
A, two kinds of monomers of c and catalyzer Cat1 are joined in the flask or reaction kettle that whipping appts and condensing works are housed according to a certain percentage; Vacuumize then, inflated with nitrogen to be to remove the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Temperature of reaction is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; (the Theoretical Calculation amount is the twice of the molar weight of monomer a) adds catalyzer Cat2, under 240～280 ℃, vacuumize (＜500Pa) stir 1～6h, stop heating, obtain polymkeric substance e.
Wherein: the mol ratio of monomer a and monomer c is 1: 12～1: 3; The weight fraction that catalyzer Cat1, Cat2 account for reactive component a and c is 0.001%～0.5%, preferred 0.005%～0.3%.Described catalyst component Cat1 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, acetate, the tosylate.
Described catalyst component Cat2 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, tin compound or the antimony compounds.
At reacting middle catalyst Cat1, Cat2, Cat3, Cat4 can be same substance, also can be different substances.
A kind of in the preferred zinc acetate of described acetate, magnesium acetate or the manganese acetate or their any mixture.
The mixture of one or more in the preferred tetra-n-butyl titanate of described titanium compound, tetraethyl titanate, metatitanic acid four n-propyls, titanium isopropylate or the metatitanic acid four different monooctyl esters;
A kind of in the preferred dibutyltin oxide of described tin compound, stannous octoate or the tin protochloride or their any mixture;
The mixture of one or both in preferred antimony acetate of described antimony compounds or the Antimony Trioxide: 99.5Min.
The polyester that the inventive method prepares vacuumizes the desired molecule amount that obtains under 240～280 ℃; In order to prevent unnecessary degraded and/or side reaction; Said method is before per step vacuumizes; Further add thermo-stabilizer, the weight fraction that the thermo-stabilizer of adding accounts for reactive component is 0.001%～2%, preferred 0.002%～1%.。
Said thermo-stabilizer is selected from a kind of or any at least two or more mixture in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate or the triethyl phosphate.
The present invention compares with prior art, possesses following advantage:
1, the biodegradable aliphatic-aromatic copolyester of the present invention's preparation has excellent performances such as mechanics, calorifics and thermodynamics, can be used for preparing products such as film, spinning, sheet material, printing ink, and products obtained therefrom has reached the requirement of actual use.
2, the invention provides the aromatic series that a kind of utilization is purchased or reclaims or the method for the degradable aliphatic-aromatic copolyester of aliphatic polyester synthesising biological; This method is compared with traditional method; Can regulate aliphatics unit and the unitary ratio of aromatic series in biodegradable aliphatic-aromatic copolyester easily; Particularly exactly can be purchased, recovery even synthetic product carry out " secondary is synthetic "; Thereby regulate the performances such as mechanics, calorifics and biological degradability of gained copolyesters, obtain meeting the biodegradable copolyester product of desired properties requirement.
3, the method for this aromatic series that is purchased or reclaims capable of using provided by the invention or the degradable aliphatic-aromatic copolyester of aliphatic polyester synthesising biological; Especially use aromatic series or the aliphatic polyester product that reclaims; Compare with traditional method; Can well solve the expensive problem (the reclaimed materials cost is lower) of aliphatic-aromatic copolyester products material cost, thereby reduce the higher selling price of present aliphatic-aromatic copolyester product to a great extent.Played positive pushing effect for large-scale the popularizing of this biodegradable copolyester; Meanwhile; Being widely used of this biodegradable copolyester product will be reduced the usage quantity of traditional " disposable " plastics, alleviated the pressure of environment protection greatly.
4, the aromatic series that is purchased or reclaims this capable of using of the present invention's use or the method for the degradable aliphatic-aromatic copolyester of aliphatic polyester synthesising biological; Especially use the aromatic polyester product that reclaims; It is the green process that turns waste into wealth; The aromatic polyester product recycling that this process is difficult to occurring in nature to degrade, and be processed into biodegradable aromatic-aliphatic copolyester to them, the rubbish that this is equivalent to help environment to dispose and is difficult to digest.For alleviating environmental stress, protection environment aspect is extremely important.
Embodiment
Below in conjunction with embodiment the present invention is further described.
In the following embodiment that provides, adopt following detection method:
Under 150 ℃ or 220 ℃ and 2.16kg according to ASTM D 1238-89 canonical measure melt mass flow rate MFR:
Adopt differential scanning calorimeter Perkin Elmer DSC7, under following type of heating, measure second-order transition temperature T
gWith melt temperature T
m:
Scanning with 50 ℃/min, is warming up to 250 ℃ from-100 ℃ for the first time;
Scanning with 10 ℃/min, is cooled to-100 ℃ from 250 ℃ for the second time;
Scanning with 20 ℃/min, is warming up to 250 ℃ from-100 ℃ for the third time.
Density:
The analytical balance Sartorius AC 120S that employing is equipped with Sartoius Kit YDK 01 carries out the density measurement according to Mohr Westphal method.This balance is kept at room temperature, and each test is approximately being carried out under the 2g polymer samples.
Weight-average molecular weight M
wIn Waters 600E series GPC system, measure, wherein chloroform is used for working curve as elutriant and polystyrene standard sample.
Biodegradability:
Test with controlled composting processing biodegrade according to standard ISO 14855amendment 1.Sample is cut into the print that area is 2cm * 2cm through hot pressing film forming (10～20 μ m), imbeds in the petridish that composting soil is housed, and puts into the incubator of fixed temperature and humidity together, keeps humidity about 50%, temperature (58 ± 2) ℃.Its surface topography is observed and write down to the weightlessness of period sampling measuring sample.
Embodiment 1
The 41g polytrimethylene terephthalate (is purchased M
w=10000g/mol), 35g Succinic Acid, 55g 1, ammediol, 0.04g titanium isopropylate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification and transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 215 ℃ and stir 4h, in this process; Water as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of Succinic Acid molar weight)
0.03g stannous octoate, 0.05g triethyl phosphate join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 270 ℃ temperature and stirs 2h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the Succinic Acid 1 of ammediol-(60%mol), ammediol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 84100, T
g=-25 ℃, T
m=137 ℃, elongation at break is 1370%, and US is 18MPa, and MFR (150 ℃, 2.16kg)=10.1g/10min, density is 1.23g/cm
3, biological degradation rate is 48%.
Embodiment 2
The 91g polyhexamethylene adipate (is purchased M
w=5000g/mol), 19g DMT. Dimethyl p-benzenedicarboxylate (DMT), 30g 1,6-pinakon, 0.03g antimony acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 230 ℃ and stir 4h, in this process; Methyl alcohol as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(methyl alcohol Theoretical Calculation amount is the twice of DMT molar weight)
0.02g dibutyltin oxide, 0.04g trimethyl phosphite 99 join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 250 ℃ temperature and stirs 6h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 6-pinakon-(80%mol), 6-pinakon copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 83800, T
g=-46 ℃, T
m=59 ℃, elongation at break is 1850%, and US is 19MPa, and MFR (150 ℃, 2.16kg)=19.3g/10min, density is 121g/cm
3, biological degradation rate is 92%.
Embodiment 3
With 1 of 44g polybutylene terephthalate (reclaim, molecular weight unknown), 44g hexanodioic acid, 70g, 4-butyleneglycol, 0.04g titanium isopropylate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification and transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 230 ℃ and stir 3.5h, in this process; Water as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of hexanodioic acid molar weight)
0.04g Antimony Trioxide: 99.5Min, 0.04g triethyl-phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 270 ℃ temperature and stirs 2h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 4-butyleneglycol-(60%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 76200, T
g=-38 ℃, T
m=108 ℃, elongation at break is 1530%, and US is 18MPa, and MFR (150 ℃, 2.16kg)=11.3g/10min, density is 121g/cm
3, biological degradation rate is 94%.
Embodiment 4
40g is gathered 1 of hexanodioic acid fourth diester (reclaim, molecular weight unknown), 58g DMT. Dimethyl p-benzenedicarboxylate (DMT), 72g, and 4-butyleneglycol, 0.04g antimony acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 225 ℃ and stir 3h, in this process; Methyl alcohol as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(methyl alcohol Theoretical Calculation amount is the twice of DMT molar weight)
0.03g stannous octoate, 0.03g triphenyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 265 ℃ temperature and stirs 1.5h, stops heating.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets the hexanodioic acid 1 of poly terephthalic acid 1,4 butyleneglycol-(40%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 74700, T
g=-23 ℃, T
m=155 ℃, elongation at break is 1340%, and US is 25MPa, and MFR (190 ℃, 2.16kg)=24.1g/10min, density is 1.25g/cm
3, biological degradation rate is 83%.
Embodiment 5
With 1 of 49g DMT. Dimethyl p-benzenedicarboxylate (DMT), 55g, 4-butyleneglycol, 0.03g tetra-n-butyl titanate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee transesterification reaction.Transesterification reaction stirs 2h at 220 ℃, and in this process, methyl alcohol is steamed from reaction mixture as sub product, reaches 92% of Theoretical Calculation amount until the amount of cut liquid.(methyl alcohol Theoretical Calculation amount is the twice of DMT molar weight)
0.02g tetra-n-butyl titanate, 0.04g triphenyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 260 ℃ temperature and stirs 2h, stops heating.
In reaction system, add 37g hexanodioic acid, 55g 1,4-butyleneglycol, 0.03g tetra-n-butyl titanate vacuumize, inflated with nitrogen three times; The oxygen of removing in the reaction unit carries out under condition of nitrogen gas to guarantee esterification and transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 230 ℃ and stir 3h, in this process; Water as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of hexanodioic acid molar weight)
0.02g tetra-n-butyl titanate, 0.04g triphenyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 260 ℃ temperature and stirs 1.5h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 4-butyleneglycol-(50%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 74200, T
g=-32 ℃, T
m=131 ℃, elongation at break is 1360%, and US is 23MPa, and MFR (150 ℃, 2.16kg)=11.9g/10min, density is 1.23g/cm
3, biological degradation rate is 95%.
Embodiment 6
Terepthaloyl moietie, the 0.03g zinc acetate of 40g sebacic acid, 25g are joined in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification.Esterification stirs 4h at 200 ℃, and in this process, water is steamed from reaction mixture as sub product, reaches 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of sebacic acid molar weight)
0.02g tin protochloride, 0.03g trimethyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 255 ℃ temperature and stirs 2h, stops heating.
The DMT. Dimethyl p-benzenedicarboxylate (DMT), the dimethyl isophthalate of 6g, the terepthaloyl moietie of 47g, the 0.03g zinc acetate that in reaction system, add 52g; Vacuumize, inflated with nitrogen three times; The oxygen of removing in the reaction unit carries out under condition of nitrogen gas to guarantee transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 200 ℃ and stir 2.5h, in this process; Methyl alcohol as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(methyl alcohol Theoretical Calculation amount is the twice of rutgers molar weight)
0.02g tin protochloride, 0.03g triphenylphosphate join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 260 ℃ temperature and stirs 2.5h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets the sebacic acid terepthaloyl moietie copolyesters of the m-phthalic acid terepthaloyl moietie of poly terephthalic acid terepthaloyl moietie-(6%mol)-(40%mol).
The gained copolyesters is through detecting, and its weight-average molecular weight is 68100, T
g=-15 ℃, T
m=175 ℃, elongation at break is 1250%, and US is 22MPa, and MFR (220 ℃, 2.16kg)=42.2g/10min, density is 1.25g/cm
3, biological degradation rate is 74%.
Embodiment 7
With the product poly terephthalic acid 1 of 53g embodiment 5, the hexanodioic acid 1 of 4-butyleneglycol-(50%mol), 1 of 4-butyleneglycol copolyesters, 37g hexanodioic acid, 60g, 4-butyleneglycol, 0.04g metatitanic acid four n-propyls join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas with the assurance esterification/ester exchange reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 230 ℃ and stir 4h, in this process; Water as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of hexanodioic acid molar weight)
0.03g tetra-n-butyl titanate, 0.04g triphenylphosphate join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 255 ℃ temperature and stirs 2h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 4-butyleneglycol-(75%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 79300, T
g=-50 ℃, T
m=39 ℃, elongation at break is 2240%, and US is 14MPa, and MFR (150 ℃, 2.16kg)=31.3g/10min, density is 1.19g/cm
3, biological degradation rate is 99%.
Embodiment 8
Product poly terephthalic acid 1 with 53g embodiment 5; The hexanodioic acid 1 of 4-butyleneglycol-(50%mol); 1 of 4-butyleneglycol copolyesters, 49g DMT. Dimethyl p-benzenedicarboxylate (DMT), 55g, 4-butyleneglycol, 0.04g magnesium acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 200 ℃ and stir 2.5h, in this process; Methyl alcohol as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(methyl alcohol Theoretical Calculation amount is the twice of DMT molar weight)
0.05g tin protochloride, 0.04g trimethyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 275 ℃ temperature and stirs 3h, stopped reaction.
Reaction mixture is taken out from bottle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 4-butyleneglycol-(25%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 75700, T
g=-4 ℃, T
m=192 ℃, elongation at break is 330%, and US is 47MPa, and MFR (220 ℃, 2.16kg)=35.1g/10min, density is 1.27g/cm
3, biological degradation rate is 32%.
Embodiment 9
With 1 of 1660g terephthalic acid (PTA), 2000g, 4-butyleneglycol, 0.7g tetra-n-butyl titanate join in the reaction kettle of 15L.After all material added, the oxygen in the reaction kettle was removed in inflated with nitrogen, venting.Carry out under condition of nitrogen gas to guarantee esterification.Esterification stirs 3h at 230 ℃, and in this process, water is steamed from reaction mixture as sub product, reaches 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of PTA molar weight)
1.0g tin protochloride, 11g triphenyl phosphite join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 260 ℃ temperature and stirs 1.5h, stops heating.In reaction system, add 1460g hexanodioic acid, 2100g 1,4-butyleneglycol, 0.6g metatitanic acid four n-propyls, inflated with nitrogen, venting; The oxygen of removing in the reaction kettle carries out under condition of nitrogen gas to guarantee esterification and transesterification reaction; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, be reflected at 230 ℃ and stir 4h, in this process; Water as sub product from reaction mixture by being steamed, reach 92% of Theoretical Calculation amount until the amount of cut liquid.(the water theory calculated amount is the twice of hexanodioic acid molar weight)
0.7g Antimony Trioxide: 99.5Min, 1.0g triethyl phosphate join in the reaction mixture as catalyzer, the thermo-stabilizer of polycondensation respectively.Polyreaction vacuumizes under 260 ℃ temperature and stirs 2h, stopped reaction.
Reaction mixture is taken out from reaction kettle, and cooling forming in water promptly gets poly terephthalic acid 1, the hexanodioic acid 1 of 4-butyleneglycol-(50%mol), 4-butyleneglycol copolyesters.
The gained copolyesters is through detecting, and its weight-average molecular weight is 69400, T
g=-33 ℃, T
m=130 ℃, elongation at break is 1320%, and US is 22MPa, and MFR (150 ℃, 2.16kg)=13.1g/10min, density is 1.23g/cm
3, biological degradation rate is 96%.
Implementation process and detected result through each embodiment; Can know by preparation method of the present invention and can conveniently regulate aliphatics unit and the unitary ratio of aromatic series in the aliphatic-aromatic copolyester, for the polymkeric substance that obtains having required specified property provides a method very easily.And can utilize existing aliphatics or aromatic polyester finished product, reduce the co-polyester production cost, improved the polyester plastics recovery utilization rate.
Above-mentioned description to embodiment is can understand and use the present invention for the ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. the preparation method of a biodegradable aliphatic-aromatic copolyester, it is characterized in that: this method may further comprise the steps,
Polymkeric substance d and a monomer or polymkeric substance e and b monomer are joined in the flask or reaction kettle that whipping appts and condensing works are housed with c monomer and catalyzer Cat3 together according to a certain percentage; Vacuumize, inflated with nitrogen removes the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Control reaction temperature is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; Add catalyzer Cat4, under 240～280 ℃, vacuumize and stir 1～6h, stopped reaction;
Wherein: monomer a is selected from one or more the mixture in aromatic acid, ester or the acid anhydrides; Monomer b is selected from one or more the mixture in aliphatic dibasic acid, ester or the acid anhydrides; Monomer c is selected from one or more the mixture in aliphatic dihydroxy alcohol or the alicyclic divalent alcohol; Polymkeric substance d is selected from one or more the mixture in aliphatic polyester or the aromatic-aliphatic copolyester, and wherein the aliphatic poly ester units accounts for more than 50% of total amount in the copolyesters; Polymkeric substance e is selected from one or more the mixture in aromatic polyester or the aromatic-aliphatic copolyester, and wherein the aromatic polyester unit accounts for more than 50% of total amount in the copolyesters; The mol ratio of diprotic acid unit and monomer a is 90: 10～0: 100 among the polymkeric substance d; The mol ratio of monomer a and monomer c is 1: 1.2～1: 3; The mol ratio of diprotic acid unit and monomer b is 90: 10～0: 100 among the polymkeric substance e; The mol ratio of monomer b and monomer c is 1: 1.2～1: 3; The weight fraction that catalyzer Cat3, Cat4 account for reactive component a, b and c is 0.001%～0.5%; Catalyzer Cat3, Cat4 are for having the conventional catalyst of katalysis to transesterify and/or esterification.
2. method according to claim 1 is characterized in that: described aromatic acid is selected from one or more the mixture in terephthalic acid, m-phthalic acid, phthalic acid or the naphthalic acid; Described aromatic dicarboxylic ester is selected from DMT. Dimethyl p-benzenedicarboxylate; The terephthalic acid diethyl ester; Terephthalic acid di ester; Terephthalic acid diisobutyl ester; Terephthalic acid two n-pentyl esters; Terephthalic acid di neo-pentyl ester; Terephthalic acid di-n-hexyl ester; Dimethyl isophthalate; The m-phthalic acid diethyl ester; M-phthalic acid di ester; M-phthalic acid diisobutyl ester; M-phthalic acid two n-pentyl esters; M-phthalic acid di neo-pentyl ester; M-phthalic acid di-n-hexyl ester; Dimethyl phthalate; The phthalic acid diethyl ester; Phthalic acid di ester; O-benzene butyl phthalate ester; Phthalic acid two n-pentyl esters; Phthalic acid di neo-pentyl ester; Phthalic acid di-n-hexyl ester; Naphthalene diformic acid dimethyl ester; The naphthalic acid diethyl ester; Naphthalic acid di ester; Naphthalic acid diisobutyl ester; Naphthalic acid two n-pentyl esters; The mixture of one or more in naphthalic acid di neo-pentyl ester or the naphthalic acid di-n-hexyl ester; Described aromatic dicarboxylic anhydride is selected from one or more the mixture in terephthalic anhydride, Tetra hydro Phthalic anhydride or the isophthalic anhydride.
3. method according to claim 1 is characterized in that: described aliphatic dibasic acid is selected from C
2～C
15Straight chain aliphatic dibasic acid or C
5～C
10The alicyclic diprotic acid of ring-type in one or more mixture; Described binary aliphatic ester is selected from aliphatic dibasic acid C
1-C
6Alkyl ester; Described binary aliphatic acid anhydrides is selected from one or more the mixture in oxalic acid acid anhydride, Succinic anhydried or the adipic anhydride.
4. method according to claim 1 is characterized in that: described aliphatic dihydroxy alcohol is selected from C
2～C
13Alkanediol; Described alicyclic divalent alcohol is selected from C
5～C
10The cycloalkanes glycol; Described aliphatic polyester is selected from the polyglycerol fatty acid ester by linear diprotic acid and linear diols preparation; Described aromatic polyester is selected from the poly aromatic acid esters by terephthalic acid and linear diols preparation; Described aromatic-aliphatic copolyester is selected from by one or more the mixture in the poly aromatic acid-lipid acid copolyesters of terephthalic acid or linear diprotic acid and linear diols preparation.
5. method according to claim 1 is characterized in that: described catalyst component Cat3 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, acetate or the toluene-4-sulfonic acid; Described catalyst component Cat4 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, tin compound or the antimony compounds.
6. method according to claim 1; It is characterized in that: described polymkeric substance d is further prepared by following method; This method may further comprise the steps, and b, two kinds of monomers of c and catalyzer Cat1 are joined in the flask or reaction kettle that whipping appts and condensing works are housed according to a certain percentage, vacuumizes then, inflated with nitrogen to be to remove the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Temperature of reaction is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; Add catalyzer Cat2, under 240～280 ℃, vacuumize and stir 1～6h, stop heating, obtain polymkeric substance d;
Wherein: the mol ratio of monomer b and monomer c is 1: 12～1: 3; The weight fraction that catalyzer Cat1, Cat2 account for reactive component b and c is 0.001%～0.5%; Described catalyzer Cat1, Cat2 are for having the conventional catalyst of katalysis to transesterify and/or esterification.
7. method according to claim 1 is characterized in that: described polymkeric substance e is further prepared by following method, and this method may further comprise the steps,
A, two kinds of monomers of c and catalyzer Cat1 are joined in the flask or reaction kettle that whipping appts and condensing works are housed according to a certain percentage; Vacuumize then, inflated with nitrogen to be to remove the oxygen in the reaction unit; Assurance transesterify and/or esterification are carried out under condition of nitrogen gas; Temperature of reaction is 170～230 ℃, is stirring, is reacting under the condensing condition, reaches more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification; Add catalyzer Cat2, under 240～280 ℃, vacuumize and stir 1～6h, stop heating, obtain polymkeric substance e;
Wherein: the mol ratio of monomer a and monomer c is 1: 1.2～1: 3; The weight fraction that catalyzer Cat1, Cat2 account for reactive component a and c is 0.001%～0.5%; Catalyzer Cat1, Cat2 are for having the conventional catalyst of katalysis to transesterify and/or esterification.
8. according to claim 6 or 7 described methods, it is characterized in that: described catalyst component Cat1 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, acetate or the tosylate; Described catalyst component Cat2 is selected from a kind of or any two kinds mixture or three kinds the mixture in titanium compound, tin compound or the antimony compounds.
9. according to claim 1,6 or 7 described methods, it is characterized in that: said method further added thermo-stabilizer before per step vacuumizes, and the weight fraction that the thermo-stabilizer of adding accounts for reactive component is 0.001%～2%.
10. method according to claim 9 is characterized in that: said thermo-stabilizer is selected from a kind of or any at least two or more mixture in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate or the triethyl phosphate.
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| CN102485766A (en) * | 2010-12-02 | 2012-06-06 | 上海杰事杰新材料(集团)股份有限公司 | Aliphatic / aromatic copolyester and preparation method thereof |
| CN102828276A (en) * | 2012-09-04 | 2012-12-19 | 福建鑫华股份有限公司 | Preparation method of biodegradable regenerated polyester staple fibers |
| CN104558549A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A preparing method of aliphatic/aromatic copolyester |
| CN110776624A (en) * | 2019-10-24 | 2020-02-11 | 彤程化学（中国）有限公司 | Antistatic biodegradable aliphatic-aromatic copolyester nano composite material and preparation method thereof |
| CN111848936A (en) * | 2020-08-11 | 2020-10-30 | 广州德恒致远科技有限公司 | Biodegradable copolyester and preparation method thereof |
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| CN114805779A (en) * | 2022-05-05 | 2022-07-29 | 浙江大学 | Method for synthesizing aromatic-aliphatic copolyester from aromatic polyester and product thereof |
| CN115558092A (en) * | 2022-10-09 | 2023-01-03 | 化学与精细化工广东省实验室 | Recycling method of waste PET and biodegradable copolyester prepared by adopting recycling method |
| CN115572377A (en) * | 2022-10-13 | 2023-01-06 | 北京化工大学 | Method for synthesizing polyester elastomer by recycling aromatic polyester plastic and polyester elastomer |
| CN117417516A (en) * | 2023-12-19 | 2024-01-19 | 康辉新材料科技有限公司 | Preparation method of terephthalyl alcohol molecular structure modified PBAT |
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| CN102828276A (en) * | 2012-09-04 | 2012-12-19 | 福建鑫华股份有限公司 | Preparation method of biodegradable regenerated polyester staple fibers |
| CN102828276B (en) * | 2012-09-04 | 2014-06-25 | 福建鑫华股份有限公司 | Preparation method of biodegradable regenerated polyester staple fibers |
| CN104558549A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A preparing method of aliphatic/aromatic copolyester |
| CN110776624A (en) * | 2019-10-24 | 2020-02-11 | 彤程化学（中国）有限公司 | Antistatic biodegradable aliphatic-aromatic copolyester nano composite material and preparation method thereof |
| CN111848936B (en) * | 2020-08-11 | 2023-04-18 | 江苏睿安应用生物技术股份有限公司 | Biodegradable copolyester and preparation method thereof |
| CN111848936A (en) * | 2020-08-11 | 2020-10-30 | 广州德恒致远科技有限公司 | Biodegradable copolyester and preparation method thereof |
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| CN114805779A (en) * | 2022-05-05 | 2022-07-29 | 浙江大学 | Method for synthesizing aromatic-aliphatic copolyester from aromatic polyester and product thereof |
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| CN115572377A (en) * | 2022-10-13 | 2023-01-06 | 北京化工大学 | Method for synthesizing polyester elastomer by recycling aromatic polyester plastic and polyester elastomer |
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