CN101020746A - Prepn process of biodegradable polyamidoester - Google Patents
Prepn process of biodegradable polyamidoester Download PDFInfo
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- CN101020746A CN101020746A CNA2007100645355A CN200710064535A CN101020746A CN 101020746 A CN101020746 A CN 101020746A CN A2007100645355 A CNA2007100645355 A CN A2007100645355A CN 200710064535 A CN200710064535 A CN 200710064535A CN 101020746 A CN101020746 A CN 101020746A
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Abstract
The present invention is preparation process of biodegradable polyamidoester. Dibasic alcohol and dibasic acid are first melt polycondensated to prepare low molecular weight polyester pre-polymer with number average molecular weight of 2000-9700 or inherent viscosity below 0.5; and the low molecular weight polyester pre-polymer is then melt and chain expanded with binary fatty oxazoline or binary aromatic oxazoline in the presence of chain expander to prepare biodegradable polyamidoester with number average molecular weight up to 39 KD and inherent viscosity up to 1.25 dL/g.
Description
Technical field
The present invention relates to a kind of preparation method of aliphatic polyester, be specifically related to prepare the preparation method of biodegradable polyamidoester, particularly adopt polycondensation, chain extension two-step approach prepare number-average molecular weight 2.0～3.9 ten thousand, limiting viscosity is in the method for the high molecular biodegradable polyamidoester of 0.69～1.25dL/g.
Background technology
Adopting polycondensation, chain extension legal system to be equipped with aliphatic polyester is disclosed method, this method prepares the aliphatic polyester performed polymer of lower molecular weight or limiting viscosity earlier by polycondensation, again with the chainextender chain extension, wherein performed polymer structure, chainextender select and chain extension method very big to the quality influence of the reaction process of synthetic different products and product, as: it is chainextender that the flat 6-322091 of the open communique of Japanese Patent adopts tetraprotic acid dicarboxylic anhydride, flat 6-256461 to adopt vulcabond, 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.Prepare hydroxyl telechelic polyester performed polymer (oligopolymer) by polycondensation in Chinese patent 200510093775.9 applications; carry out chain extension with two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl; the preparation number-average molecular weight reaches 50,000 aliphatic polyester; can under the feed ratio of lower vacuum tightness and broad, carry out; be convenient to operation; but the preparation of hydroxyl telechelic polyester performed polymer is still comparatively loaded down with trivial details, consuming time, and this method synthetic is the aliphatic polyester that does not contain polyamide structure.
Biodegradable polyamidoester belongs to the special aliphatic poly ester material of a class, and main preparation methods is to adopt the preparation of polycondensation method at present.In WO 42514 (1999), the WO 28371 (1999) of (Bayer companies) such as Timmermann, DE 4327024 patents, by diprotic acid, dibasic alcohol and diamine and/or hexanolactam etc., direct melt polycondensation prepares the biological degradability polyesteramide, and the content of polyamide structure wherein is often between 30～70%.In the WO 35179 (1999) of (Bayer companies) such as Timmermann, then adopt the direct condensation of polyester and polyamide prepolymer aggressiveness, the polymeric amide-polyester of synthetic block, wherein the content of polyamide structure is also between 20～80%.The structural content of polymeric amide is generally more in the polyesteramide of method for preparing, has influenced its biological degradability.In addition, owing to need to form amido linkage and ester bond simultaneously in the polycondensation process, so polymerization needs equipment to bear certain pressure in earlier stage, and the later stage needs very high vacuum tightness, to the equipment requirements height.Simultaneously, reaction often needs to carry out under 250 ℃ high temperature.Tuominen etc. are at Macromolecules, and 2000,33:3530 has reported the reaction with two (2-oxazoline) chain extension poly(lactic acid) performed polymer, has synthesized number-average molecular weight and can reach 74000 polylactic acid based polyesteramide.But because lactic acid polycondensation and chain extending reaction temperature higher (more than 200 ℃), be easy to cause the destruction of poly(lactic acid) tacticity, even with L-lactic acid is that raw material carries out polycondensation and chain extension, the poly(lactic acid) that obtains at last also is unformed fully, can't obtain good poly-(L-lactic acid) the based polyamide ester of good crystallinity, performance.
Summary of the invention
The present invention proposes a kind ofly to prepare the method for biodegradable polyamidoester by diprotic acid and dibasic alcohol polycondensation and chain extension, and this method performed polymer preparation is simple, and the chain extending reaction temperature is lower, stable, and the polyesteramide crystallinity and the biological degradability of preparation are good.
The present invention is by the melt polycondensation reaction of dibasic alcohol and diprotic acid, the preparation estrodur performed polymer, carry out chain extension with chainextender again, diprotic acid and dibasic alcohol 0.8～1.5 ratio in molar ratio wherein, in the presence of catalyzer, carry out melt polycondensation reaction, the preparation number-average molecular weight 2000～9700 or limiting viscosity at the terminal carboxyl polyester performed polymer below 0.5, the polycondensation temperature is between 130～250 ℃; The Yong bisoxazoline is a chainextender then, in the presence of the chain extension catalyzer, the terminal carboxyl polyester performed polymer is carried out the catalysis chain extending reaction, the chain extending reaction temperature is between 160～200 ℃, be reflected under the normal pressure and carry out, in 100 parts of terminal carboxyl polyester performed polymers of parts by weight, the chainextender consumption is at 1～15 part, catalyst levels is at 0.01～0.5 part, described chain extension catalyzer is that tosic acid is or/and phosphorous acid, phosphoric acid, prepare number-average molecular weight at 2.0～3.9 ten thousand, or the polyesteramide of the biological degradability diprotic acid/dibasic alcohol polyester based of limiting viscosity between 0.69～1.25dL/g.
Bisoxazoline class chainextender of the present invention comprises Zhi fat family Er Yuan oxazoline and the fragrant Er Yuan of the family oxazoline of Fang.Wherein:
The Er Yuan of Zhi fat family oxazoline structure is shown in (I):
R is-(CH in the formula
2)
n-, n=0～20 wherein.The available Zhi fat Er Yuan of family oxazoline comprises: two (2-oxazolines), 1,1-two (2-oxazoline) methane, 1,2-two (2-oxazoline) ethane, 1,3-two (2-oxazoline) propane, 1,4-two (2-oxazoline) butane, 1,5-two (2-oxazoline) pentane, 1,6-two (2-oxazoline) hexane, 1,7-two (2-oxazoline) heptane, 1,8-two (2-oxazoline) octane, 1,9-two (2-oxazoline) nonane, 1,10-two (2-oxazoline) decane, 1,11-two (2-oxazoline) undecane or 1,12-two (2-oxazoline) dodecane etc.
The fragrant Er Yuan of the family oxazoline of Fang structure is shown in (II):
Ar is phenyl, pyridyl etc. in the formula, links to each other Yu the oxazoline ring by ortho position, a position or contraposition mode.The fragrant Er Yuan of the family oxazoline of available Fang comprises: 1,2-phenyl-two (2-oxazoline), 1,3-phenyl-two (2-oxazoline), 1,4-phenyl-two (2-oxazoline), and 2,3-pyridyl-two (2-oxazoline), 2,4-pyridyl-two (2-oxazoline), 2,5-pyridyl-two (2-oxazoline), 2,6-pyridyl-two (2-oxazoline), 3,4-pyridyl-two (2-oxazoline) etc.
The used raw material of synthesizing polyester performed polymer is known diprotic acid and dibasic alcohol.The general formula of diprotic acid is HOOC (CH
2)
nCOOH, wherein n=0～20.Diprotic acid commonly used is a single diprotic acid in oxalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, the sebacic acid, also can adopt mixed dibasic acid.Wherein optimum diprotic acid is Succinic Acid, hexanodioic acid and/or sebacic acid.The general formula of dibasic alcohol is HO (CH
2)
nOH, 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, 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.
Mol ratio by control diprotic acid and dibasic alcohol in the polycondensation process obtains the estrodur performed polymer that at least one end is a carboxyl.The mol ratio of diprotic acid/dibasic alcohol is lower than at 0.8 o'clock, can make the synthetic estrodur performed polymer have too many terminal hydroxy group, makes the chain extension effect reduce.The mol ratio of diprotic acid/dibasic alcohol is higher than at 1.5 o'clock, can produce the distillation of diprotic acid in synthetic performed polymer process, causes significant loss; The performed polymer molecular weight of Huo Deing can be lower simultaneously, also can increase the consumption of chainextender in follow-up chain extension process, increases cost.The mol ratio of diprotic acid/dibasic alcohol is preferably between 0.9～1.2.
The polycondensation temperature is crossed low reaction speed and is descended, and too high then side reaction increases.Best temperature range is between 140～220 ℃.
Polycondensation prepare estrodur performed polymer preferably process comprise two stages: normal pressure stage and decompression phase.At first by diprotic acid and 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, till acid number is constant substantially.Used vacuum tightness is below 10mmHg.
Using catalyzer in diprotic acid of the present invention and the dibasic alcohol polycondensation process is that polycondensation is adopted usually, comprises one or more mixing in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or the titanium isopropylate.Catalyst consumption is between 0.003%～0.5% (weight).Optimum catalyst levels is between 0.1%～0.3% (weight).
In addition, polycondensation is preferably in the nitrogen atmosphere and carries out.Also can add an amount of phosphorous acid is stablizer, prevents the generation of oxidizing reaction in the polycondensation process.The consumption of phosphorous acid is between 0.0%～0.3% (weight), and optimum consumption is between 0.0%～0.15%.
Catalyzer used in the catalysis chain extending reaction is different with the catalyzer in the polycondensation process, and catalyzer used in the polycondensation process does not have katalysis to chain extending reaction.The chain extension catalyzer is selected from the single catalyst in tosic acid, phosphorous acid, the phosphoric acid, or mixed catalyst.The optimum amount of catalyzer does not add catalyzer between 0.02～0.4 part, the chain extending reaction instability; When catalyst levels is too high, easily produce crosslinked.The using method that obtains the chain extension catalyzer of better effects is: when being used as catalyzer separately with tosic acid, just use in the chain extension process, before chain extension it is added with chainextender.With phosphorous acid, when phosphoric acid is catalyzer, promptly can in the preparation process of estrodur performed polymer, add separately, also can in the chain extension process, add separately, perhaps in performed polymer preparation and chain extension process, respectively add.With phosphorous acid or phosphoric acid and tosic acid during together as mixed catalyst, phosphorous acid or phosphoric acid add in polycondensation prepares the process of estrodur performed polymer usually, and tosic acid adds with chainextender in the chain extension process.
The optimum amount of chainextender Er Yuan oxazoline is between 2～11 parts (parts by weight) in the chain extending reaction.Consumption is crossed when hanging down, the chain extension weak effect; When too high, cost is too high, also is easy to produce gel.
Chain extending reaction carries out under the normal pressure molten state in nitrogen atmosphere.The preferred temperature of chain extending reaction is between 180～200 ℃.Temperature is low, and chain extending reaction is slow; The temperature height, polymkeric substance thermolysis, thermooxidizing are serious, and the product color is darker.
The present invention is two yuan of oxazoline reactions of two yuan of oxazolines of estrodur performed polymer and fat fat family or fragrant fragrant family chain extension of carboxyl with at least one end, preparation high-molecular weight biological degradability polyesteramide.Chain extending reaction with the Er Yuan of Zhi fat family oxazoline is example, and is as follows:
By above reaction process as seen, the reaction of oxazoline group couples together oligomer in end carboxyl by estrodur performed polymer and the chainextender, forms new ester bond and amido linkage simultaneously, obtains new polyesteramide thus.By selecting the ratio of design estrodur performed polymer structure, molecular weight and performed polymer/chainextender, can regulate, the crystallinity and the fusing point of controlling polymers.
Effect of the present invention:
By the polyamide structure that chainextender is introduced, shared ratio is lower than 15% (weight) in polyesteramide, helps the biological degradation of polymkeric substance, and the introducing of a small amount of amido linkage, can also make and produce hydrogen bond between molecular chain, thereby the physical strength of raising material is improved its over-all properties.
Prepare the terminal carboxyl polyester performed polymer than hydroxyl telechelic polyester performed polymer by polycondensation, preparation process is easier, both can reduce the consumption of dibasic alcohol, shortens the reaction times greatly, and proportion of raw materials is easier to control simultaneously.
Chain extending reaction carries out under normal pressure, temperature lower (200 ℃), and side reaction is few, and speed of response is fast, efficient.The polyesteramide of thus obtained aliphatic dibasic acid dibasic alcohol polyester based, number-average molecular weight can reach 3.9 ten thousand.For the higher poly butylene succinate of fusing point (PBS) performed polymer, the limiting viscosity of polyesteramide can reach 0.87dL/g behind the chain extension.
Embodiment:
The present invention utilizes diprotic acid and dibasic alcohol to carry out melt phase polycondensation, earlier preparation terminal carboxyl polyester performed polymer; By Er Yuan oxazoline chain extension, the preparation number-average molecular weight is at 2.0～3.9 ten thousand, or the biological degradability polyesteramide of limiting viscosity between 0.69～1.25dL/g again.The number-average molecular weight of polymkeric substance 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.
Below enumerate embodiment to the detailed description of the invention, but realization of the present invention is not limited to following examples.
Embodiment 1: the preparation of poly adipate succinic acid ester (PBA): with 50 parts of hexanodioic acids of parts by weight, 31 parts of butyleneglycols; 0.24 part Dibutyltin oxide; under nitrogen protection; be warmed up to 170 ℃ gradually from 140 ℃ and carry out polycondensation; 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; till acid number is constant substantially; obtaining number-average molecular weight is 9000, and limiting viscosity is 0.29dL/g, and acid number is the PBA performed polymer of 21.8mgKOH/g.
With 100 parts of the PBA oligopolymer (parts by weight) of preparation, 4.6 part 1,4-phenyl-two (2-oxazoline), 0.023 part tosic acid, in 200 ℃ of synthesis under normal pressure 3 hours, the number-average molecular weight of resulting polymers was 27500 under the nitrogen protection.
Embodiment 2: with 100 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 9000) of embodiment 1 preparation, 5.0 part 1; 4-phenyl-two (2-oxazoline), 0.05 part tosic acid; in 200 ℃ of synthesis under normal pressure 1.5 hours, the limiting viscosity of resulting polymers was 1.25dL/g under the nitrogen protection.
Embodiment 3: with 100 parts of PBA oligopolymer of parts by weight (number-average molecular weight is 9000) of embodiment 1 preparation, 5.1 part 1; 4-phenyl-two (2-oxazoline), 0.05 part tosic acid; in 180 ℃ of synthesis under normal pressure 3 hours, the number-average molecular weight of resulting polymers was 26300 under the nitrogen protection.
Embodiment 4: with reference to embodiment 3, and wherein 1,5.4 parts of 4-phenyl-two (2-oxazoline), 0.053 part of tosic acid, the number-average molecular weight of resulting polymers is 24200, limiting viscosity is 1.21dL/g.
Embodiment 5: with reference to embodiment 1, the mol ratio that changes hexanodioic acid and butyleneglycol is 1.02, and other conditionally completes are the same, and the composite number average molecular weight is 3600 PBA, and limiting viscosity is 0.21dL/g, and acid number is 47.8mgKOH/g.
Embodiment 6: 100 parts, 10 part 1 of synthetic PBA oligopolymer among the embodiment 5 (number-average molecular weight is 3600) parts by weight; 4-phenyl-two (2-oxazoline), 0.05 part tosic acid; in 200 ℃ of synthesis under normal pressure 1.5 hours, the limiting viscosity of resulting polymers was 0.97dL/g under the nitrogen protection.
Embodiment 7: with reference to embodiment 6,180 ℃ of synthesis under normal pressure 3 hours, the limiting viscosity of resulting polymers was 0.88dL/g.
Embodiment 8: with reference to embodiment 7, add 11 part 1, the limiting viscosity of 4-phenyl-two (2-oxazoline), resulting polymers is 1.00dL/g.
Embodiment 9: with reference to embodiment 1, the mol ratio that changes hexanodioic acid and butyleneglycol is 1.02, and adds the phosphorous acid of 0.1% (weight) therein, other conditionally completes are the same, the composite number average molecular weight is 3200 PBA, and limiting viscosity is 0.15dL/g, and acid number is 47.4mgKOH/g.
Embodiment 10: PBA oligopolymer (number-average molecular weight the is 3200) parts by weight that obtain among the embodiment 9 are 100 parts, 10 part 1; 4-phenyl-two (2-oxazoline); in 200 ℃ of synthesis under normal pressure 1 hour, the limiting viscosity of resulting polymers was 0.69dL/g under the nitrogen protection.
Embodiment 11: PBA oligopolymer (number-average molecular weight the is 3200) parts by weight that obtain among the embodiment 9 are 100 parts, 10 part 1; 4-phenyl-two (2-oxazoline), 0.06 part tosic acid; in 200 ℃ of synthesis under normal pressure 1 hour, the limiting viscosity of resulting polymers was 0.87dL/g under the nitrogen protection.
Embodiment 12: with reference to embodiment 1, add the phosphorous acid of 0.1% (weight) therein, other conditionally completes are the same, and the composite number average molecular weight is 9700 PBA, and acid number is 34.0mgKOH/g.
Embodiment 13: PBA oligopolymer (number-average molecular weight the is 9700) parts by weight that obtain among the embodiment 12 are 100 parts, 7.1 part 1,4-phenyl-two (2-oxazoline), 0.3 part of phosphorous acid, 180 ℃ of synthesis under normal pressure 3 hours, the number-average molecular weight of polymkeric substance was 39000.
Embodiment 14: with reference to embodiment 1, the mol ratio that changes hexanodioic acid and butyleneglycol is 0.95, adds the phosphorous acid of 0.06% (weight) therein, and other conditionally completes are the same, and the composite number average molecular weight is 7100 PBA, and acid number is 32mgKOH/g.100 parts of this PBA oligopolymer, 1,7.1 parts of 4-two (2-oxazoline) butane, 180 ℃ of synthesis under normal pressure 2 hours, the number-average molecular weight of polymkeric substance was 20800.
Embodiment 15: the preparation of poly butylene succinate (PBS): with 30 parts of Succinic Acid of parts by weight, 19.5 parts of butyleneglycols, 0.15 part Dibutyltin oxide, 0.39 part phosphorous acid, similar condition according to embodiment 1, obtain the PBS oligopolymer, its limiting viscosity is 0.25dL/g, and acid number is 22.3mgKOH/g.100 parts of this PBS oligopolymer, 1, the tosic acid that 4-phenyl-two (2-oxazoline) is 4.3 parts, 0.12 part, 200 ℃ of synthesis under normal pressure 1 hour, the limiting viscosity of resulting polymers was 0.87dL/g.
Embodiment 16: with reference to embodiment 15, wherein the butyleneglycol consumption is 22 parts, does not add phosphorous acid simultaneously, and other conditions are constant, obtains the PBS oligopolymer, and its limiting viscosity is 0.38dL/g, and acid number is 17.3mgKOH/g.100 parts of this PBS oligopolymer, 1, the tosic acid that 4-phenyl-two (2-oxazoline) is 4 parts, 0.1 part, 180 ℃ of synthesis under normal pressure 2 hours, the limiting viscosity of resulting polymers was 0.78dL/g.
Embodiment 17: 100 parts of PBS oligopolymer that obtains by embodiment 16,1, and the tosic acid that 4-phenyl-two (2-oxazoline) is 3.6 parts, 0.1 part, 180 ℃ of synthesis under normal pressure 2 hours, the limiting viscosity of resulting polymers was 0.82dL/g.
Claims (9)
1, a kind of preparation method of biodegradable polyamidoester, comprise melt polycondensation reaction, the preparation estrodur performed polymer, carry out chain extending reaction with chainextender again, it is characterized in that: with diprotic acid and dibasic alcohol is raw material, in the ratio of diprotic acid and dibasic alcohol mol ratio 0.8～1.5, in the presence of catalyzer, carry out melt polycondensation reaction, the preparation number-average molecular weight 2000～9700 or limiting viscosity at the terminal carboxyl polyester performed polymer below 0.5, the polycondensation temperature is between 130～250 ℃; The Yong bisoxazoline is a chainextender then, in the presence of the chain extension catalyzer, the terminal carboxyl polyester performed polymer is carried out the catalysis chain extending reaction, the chain extending reaction temperature is between 160～200 ℃, be reflected under the normal pressure and carry out, in 100 parts of terminal carboxyl polyester performed polymers of parts by weight, the chainextender consumption is at 1～15 part, catalyst levels is at 0.01～0.5 part, described chain extension catalyzer is that tosic acid is or/and phosphorous acid, phosphoric acid, prepare number-average molecular weight at 2.0～3.9 ten thousand, or the polyesteramide of the biological degradability diprotic acid/dibasic alcohol polyester based of limiting viscosity between 0.69～1.25dL/g.
According to the described preparation method of claim 1, it is characterized in that 2, the De bisoxazoline class chainextender that adopts comprises Zhi fat family Er Yuan oxazoline and the fragrant Er Yuan of the family oxazoline of Fang, wherein:
The Er Yuan of Zhi fat family oxazoline structure is shown in (I):
R is-(CH in the formula
2)
n-, n=0～20 wherein;
The fragrant Er Yuan of the family oxazoline of Fang, structure is shown in (II):
Ar is phenyl, pyridyl etc. in the formula, links to each other Yu the oxazoline ring by ortho position, a position or contraposition mode.
According to the described method of claim 1, it is characterized in that 3, used Er Yuan oxazoline chainextender is 1,4-phenyl-two (2-oxazoline), 1,4-bisoxazoline butane, 1,2-bisoxazoline ethane or two (2-oxazolines).
According to the described method of claim 1, it is characterized in that 4, described diprotic acid is Succinic Acid, hexanodioic acid or sebacic acid; Described dibasic alcohol is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol or diglycol ethylene.
According to the described method of claim 1, it is characterized in that 5, the mol ratio of diprotic acid and dibasic alcohol is between 0.9～1.2 during polycondensation; The polycondensation temperature is between 140～220 ℃.
6, according to the described method of claim 1, it is characterized in that, polycondensation comprises normal pressure stage and decompression phase, at first by diprotic acid and 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, till acid number was constant substantially, used vacuum tightness was below 10mmHg.
7, according to the described method of claim 1, it is characterized in that the catalyzer that diprotic acid and dibasic alcohol polycondensation are used is that in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or the titanium isopropylate one or more mix; Catalyst consumption is by weight percentage between 0.003%～0.5%.
According to the described method of claim 1, it is characterized in that 8, used catalyzer is a tosic acid or/and phosphorous acid in the catalysis chain extending reaction, its consumption is between 0.02～0.4 parts by weight.
According to the described method of claim 1, it is characterized in that 9, the consumption of chainextender Er Yuan oxazoline is between 2～11 parts by weight in the chain extending reaction.
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| CN105330846B (en) * | 2015-12-07 | 2017-06-06 | 中北大学 | Bio-based heat resistant polyamide and its synthetic method |
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