CN104558547A - Method for producing aliphatic biodegradable copolyester - Google Patents
Method for producing aliphatic biodegradable copolyester Download PDFInfo
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- CN104558547A CN104558547A CN201310514217.XA CN201310514217A CN104558547A CN 104558547 A CN104558547 A CN 104558547A CN 201310514217 A CN201310514217 A CN 201310514217A CN 104558547 A CN104558547 A CN 104558547A
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Abstract
The invention relates to a method for producing aliphatic biodegradable copolyester. The method is mainly used for solving the problem that toxic components are introduced by adding a chain extender to increase the intrinsic viscosity during a polymerization process after copolyester is subjected to step-esterification existing in the prior art. The problem is well solved by adopting the technical scheme comprising the following steps: (a) jointly carrying out esterification reaction on a component A and a component B as raw materials, at a reaction pressure of 0.1-0.5MPa and simultaneously esterifying in a single esterification reactor to obtain a prepolymer; (b) adding a titanium catalyst and a molecular weight regulator into the prepolymer and carrying out pre-condensation under the vacuum condition of the reaction pressure of 300-1000Pa; and (c) carrying out melt condensation-polymerization reaction under the vacuum condition of the reaction pressure less than 150Pa to obtain copolyester. The method can be applied in the manufacture of biodegradable packaging materials, films and sheets.
Description
Technical field
The present invention relates to a kind of production method for aliphatics Biodegradable Copolyester, especially a kind of without the need to substep esterification, without the need to adding the production method of chainextender.
Background technology
Aromatic polyester is as polyethylene terephtalate, polybutylene terephthalate PBT etc., substantially cannot degrade in the Nature, the nature degradation time of PET can reach 16 ~ 48 years, also do not have obvious bacterium or enzyme can corrode pure aromatic polyester, therefore " white pollution " that bring is a disaster of current facing mankind, and the research of Biodegradable material seems very urgent.Aliphatic polyester such as poly butylene succinate PBS, poly adipate succinic acid ester PBA etc. receive publicity day by day because of advantages such as its excellent biocompatibility, biological degradability, polymkeric substance and degraded product are nontoxic.
The homopolymer of aliphatic polyester has the defect of toughness deficiency in mechanical property, and its multipolymer then overcomes this defect as PBES, PBSA, PBAT etc., is suitable for the processing of the product such as film, sheet material.Its esterification by single kind diacid and glycol prepares carboxylate, and then carboxylate and other kind diacid secondary esterifications are formed oligopolymer, prepare the polyester with high-polymerization degree by carrying out to oligopolymer the glycol that transesterification reaction removes formation under heating and reduced pressure simultaneously.
A kind of method of continuous production biodegradable plastic is refer in CN201110401503.6, it uses the esterification that two step esterifications complete copolyesters, three one-step polycondensations have reacted final polymerization, in rear two one-step polycondensation reactions, add chainextender complete polymerization, the method of the continuous production of biodegradable polyesters is refer in CN200980113100.2, use single step reaction to complete esterification in method, but still isocyanates chainextender need be used to improve polymericular weight.
And in Industrial processes, the method for substep esterification has poor economy, use isocyanates chainextender that product can be caused to have certain bio-toxicity simultaneously.
Summary of the invention
Technical problem to be solved by this invention is that the substep esterification existed in prior art is less economical, and chain extension method causes the problem of product toxicity.The invention provides a kind of production method of aliphatics Biodegradable Copolyester, the method, without the need to substep esterification, does not use poisonous chainextender.Copolyesters limiting viscosity is 0.8 ~ 4.0dl/g, and Tc is between 30 DEG C ~ 105 DEG C, and bioaffinity is good.The shortcoming of prior art products can be overcome, can be used for being processed into film, sheet material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of aliphatics Biodegradable Copolyester, comprises the following steps:
A) with component A, B component for raw material, under reaction pressure is 0.1 ~ 0.5MPa condition, jointly carry out esterification, in single esterifying kettle, simultaneously esterification, obtains prepolymer;
B) in prepolymer, adding titanium catalyst, molecular weight regulator, is carry out precondensation under the vacuum condition of 300 ~ 1000Pa in reaction pressure;
C) be carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain copolyesters in reaction pressure;
Wherein, described component A is made up of the component C of molar fraction 60 ~ 100% and the component D of 0 ~ 40%; Component C to be the aliphatic diprotic acid of carbonatoms 2 ~ 12 or the acid anhydrides of described diprotic acid or described diprotic acid and carbonatoms be 1 ~ 10 the ester that formed of alcohol in any one or more; Component D to be the aliphatic diprotic acid of carbonatoms 6 ~ 12 or the acid anhydrides of described diprotic acid or described diprotic acid and carbonatoms be 1 ~ 10 the ester that formed of alcohol in any one or more; The described B component at least one that to be carbonatoms be in the aliphatic dihydroxy alcohol of 2 ~ 12.
In technique scheme, the mol ratio of component A and B component is preferably (0.5 ~ 1.25): 1.
In technique scheme, the aliphatic dibasic acid in described component C is preferably oxalic acid or has the structure of general formula (1):
（1），
Wherein, R ＇ is preferably from C
1~ C
10alkylidene group, alkenylene, one in cycloalkylidene or sub-cycloalkenyl group; At least one in the ester that the alcohol that described component C is more preferably 1 ~ 10 from oxalic acid, succinic acid, pentanedioic acid, maleic anhydride or above-mentioned diprotic acid and carbonatoms is formed, above-mentioned carbonatoms be 1 ~ 10 alcohol be more preferably the alcohol that carbonatoms is 1 ~ 4.
In technique scheme, the aliphatic diprotic acid in described component D preferably has the structure of general formula (2):
（2），
Wherein, R ＂ is preferably from C
4~ C
10alkylidene group, alkenylene, one in cycloalkylidene or sub-cycloalkenyl group; Described component D is more preferably from succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, maleic anhydride, dodecanedioic acid, 1,1-cyclohexanediacetic, Isosorbide-5-Nitrae-cyclohexanediacetic or above-mentioned diprotic acid and carbonatoms are at least one in the ester that formed of alcohol of 1 ~ 10; Above-mentioned carbonatoms be 1 ~ 10 alcohol be more preferably the alcohol that carbonatoms is 1 ~ 4.
In technique scheme, it is at least one in the alkylene dihydric alcohol of 2 ~ 12 that described B component is preferably carbonatoms; More preferably from ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, glycerol, Isosorbide-5-Nitrae butyleneglycol or 1, at least one in 6 hexylene glycols.
In technique scheme, in described step a), the temperature of esterification is preferably 180 ~ 230 DEG C, reaction time of esterification is preferably 30 ~ 150min, the temperature of step b) prepolymerization reaction is preferably 220 ~ 250 DEG C, the prepolymerization reaction time is preferably 30 ~ 60min, in step c), the temperature of polycondensation is preferably 220 ~ 250 DEG C, and polycondensation reaction time is preferably 60 ~ 150min.
In technique scheme, described titanium catalyst is preferably titanyl compound or has the one in the structure of logical formula I:
（Ⅰ），
Wherein, R
1~ R
4the all independent fatty group being preferably 1 ~ 10 carbon atom, R
1~ R
4in arbitrarily between any two can the structure of Cheng Huanru general formula (I ＇) or general formula (I ＇ ＇):
（Ⅰ＇），
（Ⅰ＇＇），
Wherein R
1', R
2', R
3' all independent preferred fatty group from 1 ~ 10 carbon atom; R
1~ R
4all independently be more preferably the alkyl of 1 ~ 10 carbon atom, carboxyl or carbonyl, R
1', R
2', R
3' all independent more preferably from the alkyl of 1 ~ 10 carbon atom, carboxyl or carbonyl; Described titanium catalyst is preferred one in titanium isopropylate, tetrabutyl titanate, acetic acid titanium, lactic acid titanium, tartrate titanium, Titanium Citrate, tartrate titanium, titanium ethylene glycolate, propylene glycol titanium, butyleneglycol titanium further.
In technique scheme, described molecular weight regulator has the structure of general formula (II):
（II），
Wherein R
5, R
6and R
7preferably except independently can not be selected from H, C for except H simultaneously
2~ C
6alkyl; Be more preferably the one in phosphoric acid, phosphoric acid ester, further preferred one in ortho-phosphoric acid, metaphosphoric acid, triethyl phosphate, diethyl phosphoric acid, monoethyl phosphate, tricresyl phosphate propyl ester, di(2-ethylhexyl)phosphate propyl ester, mono phosphoric acid ester propyl ester.
In technique scheme, described copolyesters limiting viscosity is preferably 0.8 ~ 4.0dl/g, and Tc is preferably between 30 DEG C ~ 105 DEG C, and copolyesters limiting viscosity is more preferably 1.5 ~ 2.0dl/g.
As most preferably one of scheme in technique scheme, component A is more preferably from C
2and C
4mixing acid, the mol ratio of component A and B component is more preferably 1.3 ~ 1.4, can reach the effect of collaborative esterification, improves copolyesters limiting viscosity.
As most preferably scheme two in technique scheme, component A is more preferably C
10organic acid or organic acid acetic and C
12organic acid or the mixture of organic acid acetic, the mol ratio of component A and B component is more preferably 1.45 ~ 1.55, can reach the effect of collaborative esterification, improves copolyesters limiting viscosity.
The feature that when the present invention utilizes component C, component D and B component to react, enzymatic synthesis condition is close, the temperature of reaction of applicable component C is selected to carry out esterification, utilize the temperature rise period in esterification, promote that the higher component D of esterification reaction temperature carries out esterification simultaneously, thus reach the effect of common esterification.The interpolation of component D also serves the effect relaxing side reaction, improves the limiting viscosity of gained copolyesters.
In the present invention, the limiting viscosity of copolyesters is by the test of method described in GB/T 14189-2008: limiting viscosity test uses phenol tetrachloroethane to make solvent in 60: 40 ratios are mixed, uses determination of ubbelohde viscometer at the temperature of 25 DEG C.
The present invention adopts the method for a step esterification to prepare aliphatics Biodegradable Copolyester, method good economy performance, can prepare the copolyesters of limiting viscosity 1.5 ~ 2.0dl/g.Avoid use chainextender, ensure that the bioaffinity of copolyesters, achieve good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
By 245g succinic acid, 130g hexanodioic acid and 348g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 210 DEG C, is discharged the water of reaction generation by rectifier unit, and carboxylate sampling content of carboxyl end group is 356mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 100ppm), phosphoric acid is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 45min, stop after 230 DEG C of reaction 150min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.76dL/g.
[embodiment 2]
By 187g oxalic acid, 105g succinic acid and 348g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 DEG C, is discharged the water of reaction generation by rectifier unit, and carboxylate sampling content of carboxyl end group is 323mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 150ppm), triethyl phosphate is (based on the amount of polyester generated, the weight of phosphorus atom is 60ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 240 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 60min, stop after 250 DEG C of reaction 150min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.83dL/g.
[embodiment 3]
By 210g succinic acid, 237g1,1-cyclohexanediacetic and 401g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 200 DEG C, discharged the water of reaction generation by rectifier unit, carboxylate sampling content of carboxyl end group is 273mmol/L.Normal pressure is down to after esterification terminates, add lactic acid titanium (based on the amount of the polyester generated, the weight of titanium atom is 120ppm), triethyl phosphate is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 220 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.62dL/g.
[embodiment 4]
By 174g maleic anhydride, 237g1,1-cyclohexanediacetic and 339g propylene glycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 200 DEG C, discharged the water of reaction generation by rectifier unit, carboxylate sampling content of carboxyl end group is 257mmol/L.Normal pressure is down to after esterification terminates, add titanium ethylene glycolate (based on the amount of the polyester generated, the weight of titanium atom is 120ppm), triethyl phosphate is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 220 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.53dL/g.
[embodiment 5]
By 409g dibutyl succinate, 237g1,1-cyclohexanediacetic and 401g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 200 DEG C, discharged the water of reaction generation by rectifier unit, carboxylate sampling content of carboxyl end group is 201mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 120ppm), triethyl phosphate is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 220 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.81dL/g.
[embodiment 6]
By 245g succinic acid, 130g hexanodioic acid, 160g ethylene glycol and 116g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 200 DEG C, is discharged the water of reaction generation by rectifier unit, and carboxylate sampling content of carboxyl end group is 327mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 100ppm), diethyl phosphoric acid is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 230 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 45min, stop after 240 DEG C of reaction 150min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the copolyesters that limiting viscosity is 1.74dL/g.
[comparative example 1]
By 350g succinic acid and 348g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 210 DEG C, is discharged the water of reaction generation by rectifier unit, and carboxylate sampling content of carboxyl end group is 265mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 100ppm), phosphoric acid is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 230 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the polyester that limiting viscosity is 1.47dL/g.
[comparative example 2]
By 245g succinic acid, 130g hexanodioic acid and 174g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 210 DEG C, is discharged the water of reaction generation by rectifier unit, and carboxylate sampling content of carboxyl end group is 620mmol/L.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 100ppm), phosphoric acid is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 230 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the polyester that limiting viscosity is 0.73dL/g.
[comparative example 3]
By 81g oxalic acid, 292g hexanodioic acid and 348g butyleneglycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 210 DEG C, the water of reaction generation is discharged, carboxylate sampling content of carboxyl end group >3000mmol/L, and skewness by rectifier unit.Normal pressure is down to after esterification terminates, add titanium isopropylate (based on the amount of the polyester generated, the weight of titanium atom is 100ppm), phosphoric acid is (based on the amount of polyester generated, the weight of phosphorus atom is 40ppm), vacuumize and be decompressed to system pressure lower than 1000Pa, simultaneous reactions temperature rises to 220 DEG C gradually, system pressure is reduced to lower than 150Pa after system reaction reaches 30min, stop after 230 DEG C of reaction 120min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.Obtain the polyester that limiting viscosity is 0.64dL/g.
Claims (10)
1. a production method for aliphatics Biodegradable Copolyester, comprises the following steps:
A) with component A, B component for raw material, under reaction pressure is 0.1 ~ 0.5MPa condition, jointly carry out esterification, in single esterifying kettle, simultaneously esterification, obtains prepolymer;
B) in prepolymer, adding titanium catalyst, molecular weight regulator, is carry out precondensation under the vacuum condition of 300 ~ 1000Pa in reaction pressure;
C) be carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain copolyesters in reaction pressure;
Wherein, described component A is made up of the component C of molar fraction 60 ~ 100% and the component D of 0 ~ 40%; Component C to be the aliphatic diprotic acid of carbonatoms 2 ~ 12 or the acid anhydrides of described diprotic acid or described diprotic acid and carbonatoms be 1 ~ 10 the ester that formed of alcohol in any one or more; Component D to be the aliphatic diprotic acid of carbonatoms 6 ~ 12 or the acid anhydrides of described diprotic acid or described diprotic acid and carbonatoms be 1 ~ 10 the ester that formed of alcohol in any one or more; The described B component at least one that to be carbonatoms be in the aliphatic dihydroxy alcohol of 2 ~ 12.
2. the production method of aliphatics Biodegradable Copolyester according to claim 1, is characterized in that the aliphatic diprotic acid in component C is oxalic acid or the structure with general formula (1):
（1），
Wherein, R ＇ is selected from C
1~ C
10alkylidene group, alkenylene, one in cycloalkylidene or sub-cycloalkenyl group; Aliphatic diprotic acid in component D has the structure of general formula (2):
（2），
Wherein, R ＂ is selected from C
4~ C
10alkylidene group, alkenylene, one in cycloalkylidene or sub-cycloalkenyl group; The B component at least one that to be carbonatoms be in the alkylene dihydric alcohol of 2 ~ 12.
3. the production method of aliphatics Biodegradable Copolyester according to claim 1, is characterized in that the mol ratio of component A and B component is for (0.5 ~ 1.25): 1.
4. the production method of aliphatics Biodegradable Copolyester according to claim 1, it is characterized in that component C is selected from oxalic acid, succinic acid, pentanedioic acid, maleic anhydride or above-mentioned diprotic acid and carbonatoms is at least one in the ester that formed of alcohol of 1 ~ 10; Select oneself diacid, nonane diacid, sebacic acid, dodecanedioic acid, 1,1-cyclohexanediacetic, Isosorbide-5-Nitrae-cyclohexanediacetic or above-mentioned diprotic acid and carbonatoms of component D is at least one in the ester that formed of alcohol of 1 ~ 10.
5. the production method of aliphatics Biodegradable Copolyester according to claim 1, is characterized in that B component is selected from ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, Isosorbide-5-Nitrae butyleneglycol or 1, at least one in 6 hexylene glycols.
6. the production method of aliphatics Biodegradable Copolyester according to claim 1, it is characterized in that the temperature of esterification in described step a) is 180 ~ 230 DEG C, reaction time of esterification is 30 ~ 150min; The temperature of step b) prepolymerization reaction is 220 ~ 250 DEG C, and the prepolymerization reaction time is 30 ~ 60min; In step c), polycondensation temperature is 220 ~ 250 DEG C, and polycondensation reaction time is 60 ~ 150min.
7. the production method of aliphatics Biodegradable Copolyester according to claim 1, is characterized in that the one that described titanium catalyst is titanyl compound or has in the structure of logical formula I:
（Ⅰ），
Wherein, R
1~ R
4all independently be selected from the fatty group of 1 ~ 10 carbon atom, R
1~ R
4in arbitrarily between any two can Cheng Huan.
8. the production method of aliphatics Biodegradable Copolyester according to claim 1, is characterized in that described molecular weight regulator has the structure of general formula (II):
（II），
Wherein R
5, R
6and R
7except independently can not be selected from H, C for except H simultaneously
2~ C
6alkyl.
9. the production method of aliphatics Biodegradable Copolyester according to claim 1, it is characterized in that copolyesters limiting viscosity is 0.8 ~ 4.0dl/g, Tc is between 30 DEG C ~ 105 DEG C.
10. the production method of aliphatics Biodegradable Copolyester according to claim 9, is characterized in that copolyesters limiting viscosity is 1.5 ~ 2.0dl/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
| CN109503817A (en) * | 2018-12-29 | 2019-03-22 | 河北大学 | A kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability and preparation method thereof |
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| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
| CN101508771A (en) * | 2009-03-18 | 2009-08-19 | 马世金 | Method of preparing biodegradable multicomponent copolyester |
| CN101838447A (en) * | 2010-05-25 | 2010-09-22 | 南通华盛新材料股份有限公司 | Fully-degradable polyester/inorganic nanoparticle composite material and method for preparing same |
| CN103073712A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Preparation method for polyester by using liquid titanium catalyst |
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| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
| CN101508771A (en) * | 2009-03-18 | 2009-08-19 | 马世金 | Method of preparing biodegradable multicomponent copolyester |
| CN101838447A (en) * | 2010-05-25 | 2010-09-22 | 南通华盛新材料股份有限公司 | Fully-degradable polyester/inorganic nanoparticle composite material and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866945A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | For the liquid condition titanium series catalyst of poly-succinic -co- adipic acid-butanediol ester |
| CN106867207A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The production method of low colour poly-succinic -co- adipic acid-butanediol ester |
| CN109503817A (en) * | 2018-12-29 | 2019-03-22 | 河北大学 | A kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability and preparation method thereof |
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