CN1923872A - Process for preparing high-molecular aliphatic polyester - Google Patents
Process for preparing high-molecular aliphatic polyester Download PDFInfo
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- CN1923872A CN1923872A CN 200510093775 CN200510093775A CN1923872A CN 1923872 A CN1923872 A CN 1923872A CN 200510093775 CN200510093775 CN 200510093775 CN 200510093775 A CN200510093775 A CN 200510093775A CN 1923872 A CN1923872 A CN 1923872A
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Abstract
the invention discloses a preparing method of macromolecular aliphatic polyester, which is characterized by the following: proceeding melting polycondensation for diatomic alcohol and diacid; obtaining low-molecular hydroxy polyester prepolymer with even molecule at 2000-7000 or characteristic viscosity under 0.5; adopting aliphatic diacyl dilactone amide or aromatic diacyl dilactone amide to melt to expand chain; obtaining the product.
Description
Technical field
The present invention relates to a kind of method for preparing aliphatic polyester, particularly adopt polycondensation, chain extension two-step approach to prepare the method for number-average molecular weight at 2.66～5.07 ten thousand high-molecular aliphatic polyester.
Background technology
Aliphatic polyester is can biodegradable material, can be widely used in many aspects such as medical treatment, agricultural, fishery, packing, has good mechanical property, and itself can degrade, and can not cause damage to environment.
In recent years, people adopt several different methods to obtain the high-molecular weight aliphatic polyester.Adopt common polycondensation legal system to be equipped with aliphatic polyester,, be difficult for obtaining the high-molecular weight aliphatic polyester, be difficult to satisfy performance requirement because there are side reactions such as thermolysis, thermooxidizing in the polymerization temperature height.The flat 6-59801 of the open communique of Japanese Patent adopts diprotic acid and dibasic alcohol polycondensation under condition of high vacuum degree, preparation high-molecular weight aliphatic polyester.This method will reach condition of high vacuum degree in actual production, often very high to equipment requirements.The flat 6-322091 employing of the open communique of Japanese Patent tetraprotic acid dicarboxylic anhydride, flat 6-256461 employing vulcabond are chainextender in addition, carry out chain extension, the preparation high-molecular aliphatic polyester.But diisocyanates is poisonous, and side reaction is many in the chain extension process, causes that easily branching is crosslinked, produces gel.Adopting the tetraprotic acid dicarboxylic anhydride is that chainextender also exists and produces gel, influences problem such as processibility.Other chainextender often exists problems such as preparation method's complexity.02100758.6 patent of the applicant's application proposes to make chainextender with organosilazanes, and chainextender itself is nontoxic, preparation is easy, thereby the preparation method of high-molecular aliphatic polyester is simplified.This method prepares number-average molecular weight at 28000-40000, and weight-average molecular weight is at the aliphatic polyester of 60000-130000.But this method chain extension time is longer, and often more than 10 hours, chain extension efficient is relatively low.The flat 7-330883 of the open communique of Japanese Patent adopts the two hexanolactams of paraphenylene terephthalamide that poly butylene succinate (PBS) is carried out chain extension, obtains the high-molecular weight aliphatic polyester.Wherein used PBS oligopolymer number-average molecular weight is more than 1.8 ten thousand, and this oligomer still needs very high vacuum tightness (below the 0.1mmHg) in building-up process, to the equipment requirements height.Feed ratio is wayward simultaneously, gives the synthetic certain degree of difficulty of bringing.
Summary of the invention
The present invention prepares the hydroxyl telechelic polyester performed polymer of lower molecular weight or limiting viscosity by polycondensation, again with aliphatics or aromatic series active amide class chainextender chain extension, propose a kind of less demandingly to vacuum tightness, feed ratio is easy to control, preparation is easy, the preparation method of aliphatic polyester efficiently.
The present invention at first with dibasic alcohol and diprotic acid by proper proportion, in the presence of catalyzer, prepare number-average molecular weight 2000～7000, or limiting viscosity is at the hydroxyl telechelic polyester performed polymer below 0.5 through melt phase polycondensation,
The mol ratio of dibasic alcohol and diprotic acid is between 1.05～1.5 during polycondensation, and the polycondensation temperature range is between 130～250 ℃; Carry out chain extending reaction with two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl then; wherein calculate with 50 parts of hydroxyl telechelic polyester performed polymers of parts by weight; the chainextender consumption is between 2～15 parts; the chain extending reaction temperature is carried out in the depressurized system of chain extending reaction between 0.1～50mmHg between 160～280 ℃.Prepare number-average molecular weight at 2.66～5.07 ten thousand, or the aliphatic polyester of limiting viscosity between 0.83～1.25dL/g.
Chainextender of the present invention is the two lactan of diacyl, comprises two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl, wherein:
The two lactan of aliphatics diacyl comprise the two lactan of chain aliphatics diacyl, shown in the structure (I):
M=3～12 wherein; R is-(CH
2)
n-, n=0～20 wherein.
Also comprise carbonyl di-lactame, structure is shown in (II):
M=3～12 wherein.
The two lactan of aromatic series diacyl, shown in structure (III):
M=3～12 wherein.Ar is a phenyl ring, links to each other with dicarbapentaborane by ortho position, a position or contraposition mode.
The present invention prepares the hydroxyl telechelic polyester performed polymer of lower molecular weight or limiting viscosity by polycondensation, again with aliphatics or aromatic series active amide class chainextender chain extension, and the preparation aliphatic polyester.Reduced vacuum requirements (getting final product below 10mmHg), speed of response is fast, efficient, and the preparation method is easy, and the number-average molecular weight of gained polyester can reach 5.07 ten thousand.For the higher poly butylene succinate of fusing point (PBS), its limiting viscosity can reach 1.25dL/g.
Embodiment:
The present invention utilizes diprotic acid and dibasic alcohol to carry out melt phase polycondensation, earlier preparation hydroxyl telechelic polyester performed polymer; By the two lactan chain extensions of diacyl, the preparation number-average molecular weight is at 2.66～5.07 ten thousand, or the aliphatic polyester of limiting viscosity between 0.83～1.25dL/g again.Number-average molecular weight is with gel permeation chromatography, and tetrahydrofuran (THF) is a moving phase, and room temperature is a benchmark with the polystyrene; Limiting viscosity is that organic solvent is measured with the chloroform.
The synthetic used raw material of hydroxyl telechelic polyester performed polymer is known diprotic acid and dibasic alcohol, those described in 02100758.6 patent of above-mentioned the applicant's application, and the general formula of diprotic acid is HOOC (CH
2)
nCOOH (IV), wherein n=0～20.Diprotic acid commonly used is oxalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid and/or sebacic acid etc.Single diprotic acid can be adopted, also mixed dibasic acid can be adopted.Wherein optimum diprotic acid is Succinic Acid, hexanodioic acid and/or sebacic acid.
The general formula of dibasic alcohol is HO (CH
2)
nOH (V), wherein n=2～10.Dibasic alcohol commonly used has ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol etc.Dibasic alcohol also can be the terminal hydroxy group polyoxyethylene glycol of different molecular weight, and general formula is H (OCH
2CH
2)
nOH (VI), wherein n=2～20.Dibasic alcohol can also be the various dibasic alcohol that have cycloaliphatic ring, and commonly used is 1,4-hydroxymethyl-cyclohexane etc.Single dibasic alcohol can be adopted in the actual polycondensation, also the mixing dibasic alcohol can be adopted.Wherein optimum dibasic alcohol is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol and/or glycol ether.
The mol ratio of dibasic alcohol and diprotic acid is generally at 1.05～1.5 in the polycondensation process, and the mol ratio of dibasic alcohol/diprotic acid is lower than at 1.05 o'clock, and speed of response is low; The mol ratio of dibasic alcohol/diprotic acid is higher than at 1.5 o'clock, will increase cost.The mol ratio of dibasic alcohol/diprotic acid is preferably between 1.1～1.22.
Employed temperature of reaction is between 130～250 ℃ in the polycondensation process, and best temperature range is between 140～220 ℃.Temperature is crossed low reaction speed and is descended, and too high then side reaction increases.
Polycondensation prepare the terminal hydroxy group performed polymer preferably process comprise two stages: normal pressure stage and decompression phase.At first by diprotic acid and excessive dibasic alcohol in the presence of catalyzer, the normal pressure polycondensation is collected the water that generates to 60～80% of theoretical amount; Change reliever into, continue reaction, be reduced to below 3 until acid number.Used vacuum tightness is below 10mmHg.
The Catalyst And Method that uses in the polycondensation process is to adopt usually, can use Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate, titanium isopropylate etc. to be also to make spent mixed catalyst by catalyzer separately.Catalyst consumption is between 0.003%～0.5% (weight).Consumption is lower than at 0.003% o'clock, and speed of response descends; Be higher than at 0.5% o'clock, though speed of response is very fast, the structure of performed polymer also can change sometimes, is unfavorable for the carrying out of chain extending reaction.Optimum catalyst levels is between 0.1%～0.25% (weight).
In addition, polycondensation is preferably in the nitrogen atmosphere to be carried out, and adding an amount of phosphorous acid simultaneously is stablizer, prevents the generation of oxidizing reaction in the polycondensation process.The consumption of phosphorous acid is between 0.01%～0.3% (weight), and optimum consumption is between 0.05%～0.15%.
Chainextender of the present invention is the two lactan of diacyl, comprises two types in two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl.Wherein the two lactan of aliphatics diacyl comprise:
Carbonyl di-lactame (as the II formula):
M=3～12 wherein;
And the two lactan (as the I formula) of chain aliphatics diacyl:
M=3～11 wherein, R is-(CH
2)
n-, n=0～20 wherein.
No matter be the two lactan chainextenders of the structure (I) or the aliphatics diacyl of structure (II); when the hydroxyl telechelic polyester oligomer is carried out chain extending reaction; all be by remove lactan, with the structure of aliphatics two acyls, oligomer is coupled together, make the molecular weight of polymkeric substance increase rapidly.The two lactan of available aliphatics diacyl comprise following kinds: N; the two pyrrolidone of N '-phosphinylidyne; N; the two hexanolactams of N '-phosphinylidyne; N; the two laurolactams of N '-phosphinylidyne; N; the two pyrrolidone of N '-oxalyl; N; the two hexanolactams of N '-oxalyl; N; the two laurolactams of N '-oxalyl; N; the two pyrrolidone of N '-succinyl; N; the two hexanolactams of N '-succinyl; N; the two laurolactams of N '-succinyl; N; the two pyrrolidone of N '-glutaryl; N; the two hexanolactams of N '-glutaryl; N; the two laurolactams of N '-glutaryl; N; the two pyrrolidone of N '-hexanedioyl; N, the two hexanolactams of N '-hexanedioyl; N, the two laurolactams of N '-hexanedioyl; N; the two pyrrolidone of N '-azelaoyl; N; the two hexanolactams of N '-azelaoyl; N, the two laurolactams of N '-azelaoyl; N, the two pyrrolidone of N '-sebacoyl; N; two hexanolactams of N '-sebacoyl or N; the two laurolactams of N '-sebacoyl etc., that wherein the most frequently used is N, the two hexanolactams of N '-phosphinylidyne; N; two hexanolactams of N '-succinyl or N, the two hexanolactams of N '-hexanedioyl.
The two lactan of aromatic series diacyl are as follows:
The two lactan chainextenders of the aromatic series diacyl of different structure, when the hydroxyl telechelic polyester oligomer is carried out chain extending reaction, all be by remove lactan, with the form of aromatic series two acyls, oligomer is coupled together, make the molecular weight of polymkeric substance increase rapidly.So available N; the two lactan (III) of N '-aromatic series diacyl comprise N; the two pyrrolidone of N '-phthalyl, N; the two hexanolactams of N '-phthalyl, N; the two laurolactams of N '-phthalyl, N; the two pyrrolidone of N '-isophthaloyl, N; the two hexanolactams of N '-isophthaloyl, N; the two laurolactams of N '-isophthaloyl, N; the two pyrrolidone of N '-paraphenylene terephthalamide, N; two hexanolactams of N '-paraphenylene terephthalamide or N, the two laurolactams of N '-paraphenylene terephthalamide etc.The two lactan of wherein the most frequently used aromatic series diacyl comprise N, two hexanolactams of N '-isophthaloyl or N, the two hexanolactams of N '-paraphenylene terephthalamide.
The consumption of the two lactan chainextenders of diacyl 50 parts of hydroxyl telechelic polyester performed polymers by weight calculates, between 2～15 parts.Be lower than 2 parts or when being higher than 15 parts, the chain extension weak effect.Optimum amount is between 4.0～8.9 parts.
Chain extending reaction carries out under molten state.Generally between 160～280 ℃, temperature is lower than 160 ℃ to the chain extending reaction temperature, and chain extending reaction is slow; Be higher than 280 ℃, polymkeric substance thermolysis, thermooxidizing are serious, and the product color is darker.Optimum chain extension temperature is between 200～240 ℃.
Chain extending reaction carries out in the depressurized system of 0.1～50mmHg.System pressure is too high to equipment requirements when 0.1mmHg is following; The chain extension effect is relatively poor when 50mmHg is above.System's optimum pressure is between 0.5～50mmHg.
In the chain extending reaction, calculate, add 0.028～0.21 part tosic acid, can promote the carrying out of chain extending reaction with 50 parts of hydroxyl telechelic polyester performed polymers of parts by weight.Optimum amount is between 0.063～0.10 part.
According to above-described embodiment, the present invention all can realize, below enumerate preferably embodiment to the detailed description of the invention, but realization of the present invention is not limited to following examples.
Embodiment
Embodiment 1: the preparation of poly adipate succinic acid ester (PBA): with 50 parts of hexanodioic acids of parts by weight, 37.5 parts of butyleneglycols; 0.22 part Dibutyltin oxide, 0.17 part of phosphorous acid are under nitrogen protection; be warmed up to 170 ℃ of polycondensations gradually from 140 ℃; collect to generate the water yield 70～80% after, use reliever instead, pressure is reduced to 1mmHg gradually; at 190～220 ℃ of temperature range reaction 4～5h; be reduced to below 3 until acid number, obtain the PBA oligopolymer, its number-average molecular weight is 3577.
Embodiment 2: with 50 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 3577), 8.9 parts of N of embodiment 1 preparation; the two hexanolactams of N '-hexanedioyl; under the nitrogen protection in 240 ℃ of synthesis under normal pressure 30 minutes; decompression (50mmHg is following) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 26589.
Embodiment 3: with reference to embodiment 1, the mol ratio that changes butyleneglycol and hexanodioic acid is 1.17, and other conditionally completes are the same, and the composite number average molecular weight is 5752 PBA.50 parts of PBA oligopolymer of parts by weight, 7.3 parts of N, the two hexanolactams of N '-hexanedioyl, under the nitrogen protection in 240 ℃ of synthesis under normal pressure 30 minutes, decompression (10mmHg is following) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 32843.
Embodiment 4: with reference to embodiment 1, the mol ratio that changes butyleneglycol and hexanodioic acid is 1.10, and other conditionally completes are the same, and the composite number average molecular weight is 6447 PBA.50 parts of PBA oligopolymer of parts by weight, 4.0 parts of N, the two hexanolactams of N '-paraphenylene terephthalamide, under the nitrogen protection in 220 ℃ of synthesis under normal pressure 30 minutes, decompression (5mmHg) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 30422.
Embodiment 5: with 50 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 6447) of embodiment 4 preparations; 5.0 part N; the two hexanolactams of N '-paraphenylene terephthalamide; under the nitrogen protection in 220 ℃ of synthesis under normal pressure 30 minutes; decompression (0.5mmHg) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 50733.
Embodiment 6: 50 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 6447); 6.0 part N, the two hexanolactams of N '-paraphenylene terephthalamide, under the nitrogen protection in 220 ℃ of synthesis under normal pressure 30 minutes; decompression (10mmHg is following) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 31004.
Embodiment 7: with reference to embodiment 1, the mol ratio that changes butyleneglycol and hexanodioic acid is 1.20, and other conditionally completes are the same, and the composite number average molecular weight is 4739 PBA.50 parts of PBA oligopolymer of parts by weight, 6.8 parts of N, the two hexanolactams of N '-hexanedioyl; 0.095 part tosic acid; under the nitrogen protection in 200 ℃ of synthesis under normal pressure 30 minutes, decompression (10mmHg is following) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 30582.
Embodiment 8: 50 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 4739), 7.2 parts of N, the two hexanolactams of N '-paraphenylene terephthalamide; 0.10 part tosic acid; under the nitrogen protection in 200 ℃ of synthesis under normal pressure 30 minutes, decompression reaction 1.5 hours, the number-average molecular weight of resulting polymers is 30523.
Embodiment 9: with reference to embodiment 1, the mol ratio that changes butyleneglycol and hexanodioic acid is 1.50, and other conditionally completes are the same, and the composite number average molecular weight is 2017 PBA.50 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 2017); 14.8 part N, the two hexanolactams of N '-phosphinylidyne, under the nitrogen protection in 220 ℃ of synthesis under normal pressure 30 minutes; decompression (10mmHg is following) reaction 1.5 hours, the number-average molecular weight of resulting polymers is 30160.
Embodiment 10: with reference to embodiment 1, the mol ratio of butyleneglycol and Succinic Acid is 1.20, and other conditionally completes are the same, synthetic poly butylene succinate (PBS) oligopolymer, and its limiting viscosity is 0.37dL/g.
Embodiment 11: 50 parts of PBS oligopolymer of parts by weight, and 4.5 parts of N, the two hexanolactams of N '-hexanedioyl, in 220 ℃ of decompressions (0.5mmHg) reaction 1.5 hours, the limiting viscosity of resulting polymers was 1.25dL/g under the nitrogen protection.
Embodiment 12: 50 parts of PBS oligopolymer of parts by weight, and 4.5 parts of N, the two hexanolactams of N '-hexanedioyl, 0.063 part of tosic acid, in 220 ℃ of decompression reactions 1.5 hours, the limiting viscosity of resulting polymers was 1.19dL/g under the nitrogen protection.
Embodiment 13: 50 parts of PBS oligopolymer of parts by weight, and 4.7 parts of N, the two hexanolactams of N '-paraphenylene terephthalamide, in 220 ℃ of decompression reactions 1.5 hours, the limiting viscosity of resulting polymers was 1.07dL/g under the nitrogen protection.
Embodiment 14: 50 parts of PBS oligopolymer of parts by weight, and 4.7 parts of N, the two hexanolactams of N '-paraphenylene terephthalamide, 0.066 part of tosic acid, in 220 ℃ of decompression reactions 1.5 hours, the limiting viscosity of resulting polymers was 0.83dL/g under the nitrogen protection.
Claims (9)
1, a kind of method for preparing high-molecular aliphatic polyester, melt polycondensation reaction by dibasic alcohol and diprotic acid, preparation hydroxyl telechelic polyester performed polymer, carry out chain extension with the two lactan of diacyl again, preparation high-molecular weight aliphatic polyester, it is characterized in that: at first adopt dibasic alcohol and diprotic acid polycondensation, the preparation number-average molecular weight is at 2000～7000, or limiting viscosity is at the hydroxyl telechelic polyester performed polymer below 0.5; The mol ratio of dibasic alcohol and diprotic acid is between 1.05～1.5 during polycondensation, and the polycondensation temperature range is between 130～250 ℃; Carry out chain extending reaction with two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl then; wherein calculate with 50 parts of hydroxyl telechelic polyester performed polymers of parts by weight; the chainextender consumption is between 2～15 parts; the chain extending reaction temperature is carried out in the depressurized system of chain extending reaction between 0.1～50mmHg between 160～280 ℃.
According to the described method of claim 1, it is characterized in that 2, the two lactan chainextenders of diacyl of the present invention comprise two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl, wherein:
The two lactan of aliphatics diacyl comprise: the two lactan of chain aliphatics diacyl, and structure is shown in (I):
M=3～12 wherein; R is-(CH
2)
n-, n=0～20 wherein,
Also comprise carbonyl di-lactame, structure is shown in (II):
M=3～12 wherein;
The two lactan of aromatic series diacyl, structure is shown in (III):
M=3～12 wherein, Ar is a phenyl ring, links to each other with dicarbapentaborane by ortho position, a position or contraposition mode.
According to the described method of claim 1, it is characterized in that 3, the mol ratio of dibasic alcohol and diprotic acid is between 1.1～1.22 during polycondensation.
According to claim 1,3 described methods, it is characterized in that 4, used dibasic alcohol and diprotic acid are butyleneglycol and Succinic Acid and/or hexanodioic acid during polycondensation.
5, according to the described method of claim 1, it is characterized in that, during chain extending reaction, 50 parts of hydroxyl telechelic polyester performed polymers of parts by weight, the consumption of the two lactan chainextenders of diacyl is between 4.0～8.9 parts.
According to claim 1,5 described methods, it is characterized in that 6, the two lactan chainextenders of used diacyl are N, the two hexanolactams of N '-hexanedioyl, N, two hexanolactams of N '-phosphinylidyne or N, the two hexanolactams of N '-paraphenylene terephthalamide.
According to the described method of claim 1, it is characterized in that 7, the chain extending reaction temperature is between 200～240 ℃.
8, according to the described method of claim 1, it is characterized in that, in chain extending reaction, calculate, add 0.063～0.10 part tosic acid with 50 parts of hydroxyl telechelic polyester performed polymers of parts by weight.
9, according to the described method of claim 1, it is characterized in that the process that polycondensation prepares the terminal hydroxy group performed polymer comprises two stages: normal pressure stage and decompression phase, at first by diprotic acid and excessive dibasic alcohol in the presence of catalyzer, the normal pressure polycondensation is collected the water that generates and is arrived 60～80% of theoretical amount; Change reliever into, used vacuum tightness continues reaction below 10mmHg, be reduced to below 3 until acid number.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101977963A (en) * | 2008-03-28 | 2011-02-16 | 三菱化学株式会社 | Production method of aliphatic polyester |
| CN101585915B (en) * | 2008-05-23 | 2011-04-20 | 北京化工大学 | Method for preparing biodegradable polyesteramide through chain extension |
| CN101367983B (en) * | 2007-08-16 | 2011-05-11 | 广州金发科技股份有限公司 | Aliphatic polyester complexes and method of preparing the same |
| CN102643422A (en) * | 2011-02-21 | 2012-08-22 | 北京化工大学 | Preparation method for biodegradable aliphatic alternating polyester amide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63265964A (en) * | 1987-04-24 | 1988-11-02 | Polyplastics Co | Resin composition |
| CN1206258C (en) * | 1997-04-22 | 2005-06-15 | Dsmip财产有限公司 | High molecular polyamide |
| NL1014604C2 (en) * | 2000-03-10 | 2001-09-11 | Dsm Nv | Procedure for chain extension. |
| EP1132411A1 (en) * | 2000-03-10 | 2001-09-12 | Dsm N.V. | Thermosetting composition |
| CN1247654C (en) * | 2002-01-23 | 2006-03-29 | 北京化工大学 | Process for preparing fatty polyester |
-
2005
- 2005-08-31 CN CNB2005100937759A patent/CN100465207C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367983B (en) * | 2007-08-16 | 2011-05-11 | 广州金发科技股份有限公司 | Aliphatic polyester complexes and method of preparing the same |
| CN101977963A (en) * | 2008-03-28 | 2011-02-16 | 三菱化学株式会社 | Production method of aliphatic polyester |
| CN101977963B (en) * | 2008-03-28 | 2013-03-27 | 三菱化学株式会社 | Production method of aliphatic polyester |
| CN101585915B (en) * | 2008-05-23 | 2011-04-20 | 北京化工大学 | Method for preparing biodegradable polyesteramide through chain extension |
| CN102643422A (en) * | 2011-02-21 | 2012-08-22 | 北京化工大学 | Preparation method for biodegradable aliphatic alternating polyester amide |
Also Published As
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| CN100465207C (en) | 2009-03-04 |
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