CN100558787C - A kind of preparation method of full biodegradation polyester copolymer - Google Patents
A kind of preparation method of full biodegradation polyester copolymer Download PDFInfo
- Publication number
- CN100558787C CN100558787C CNB2007100445077A CN200710044507A CN100558787C CN 100558787 C CN100558787 C CN 100558787C CN B2007100445077 A CNB2007100445077 A CN B2007100445077A CN 200710044507 A CN200710044507 A CN 200710044507A CN 100558787 C CN100558787 C CN 100558787C
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- molecular weight
- reaction
- acid
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of full biodegradation polyester copolymer.The present invention adopts the method for fusion direct condensation to prepare the lactic acid prepolymer of carboxy blocking, then carries out copolymerization with the aliphatic polycarbonate dibasic alcohol again, and then react in twin screw extruder and extrude chain extension, the copolymer of poly lactic acid that processability is good.Concrete steps are: lactic acid and small molecules diprotic acid react the lactic acid prepolymer of the synthetic carboxy blocking of direct condensation under the catalyzer condition, add aliphatic PCDL and catalyzer then, at N
2Under the atmosphere, vacuumize, under 150～200 ℃ of temperature, reacted 1～10 hour, obtain low molecular weight/Copolycarbonate, then in twin screw extruder under 140～190 ℃, react and extrude chain extension, finally obtain high-molecular weight, toughness and thermotolerance copolymer of poly lactic acid preferably.The inventive method technology is simple, is easy to suitability for industrialized production, the copolymer resins product fully biodegradable that makes, and Application Areas is extensive.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of full biodegradation polyester copolymer.
Background technology
Polylactic acid PLA (Poly Lactic Acid) derives from renewable resources farm crop (as corn); the most outstanding advantage is a biodegradability, and it can be degraded fully by the occurring in nature microorganism after using, and finally generates carbonic acid gas and water; free from environmental pollution, highly beneficial to the protection environment.Being extensive use of of PLA not only can be alleviated present more serious crisis of resource and environmental pollution, but also can alleviate the agricultural products in China problem of outlet.In addition, PLA also has good mechanical property, thermoplasticity, fiberizability, transparency height, is applicable to blowing, extrudes, multiple working method such as injection moulding, and easy to process, partial properties is better than materials such as existing general-purpose plastics polyethylene, polypropylene, polystyrene.As the very wide a kind of emerging biodegradable material of prospect, progressively substitute in the process of traditional petroleum-based plastics product at it, some inherent defects of PLA material itself and characteristic await to improve.At present, though there are a large amount of scholars to be engaged in the research relevant with PLA both at home and abroad, the research of its modification, processing is system perfecting not very also.
Abroad, Miller etc. discovered with oxyacetic acid and generated glycollide (glycolide the seventies, GA) again with the lactic acid ring-opening polymerization, degradation rate is improved more than 10 times than homopolymer, and can regulate the degradation speed of multipolymer by the proportioning that changes component.Nineteen eighty-three Kilpikari etc. has synthesized the multipolymer of a kind of polyglycolic acid (PGA) and PLLA (PLLA).Tormala in 1984 and Vainionpaa etc. have developed a kind of biodegradable material of self-enhancement again, the multipolymer that comprises PGA fiber reinforcement glycolic acid polymer and PGA and PLLA, the same year, Christel and Vert etc. developed the processing technology that strengthens the PLA material with the PGA fiber respectively, make to make sheet material sample initial bending modulus and rise to 6Gpa by the 4GPa before not strengthening, its makes internal fixation material of fracture that a bigger progress arranged.Employings such as David difference formula scanning amount thermal analyzer (DSC) and gel osmoticing chromatogram analysis instrument (GPC) have been studied and have been introduced the hydrolysis situation of Different Weight than PEG formation multipolymer among the PLLA, and the introducing that confirmation hydrolysis PEG is soft section has tangible influence to the degraded of PLLA.Employing multistep processes such as Korea S scholar Kim have been synthesized the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of L-rac-Lactide and L-L-glutamic acid, and it can be as the carrier of drug release.Nineteen ninety-five, it is chainextender that Woo etc. utilize hexamethylene-diisocyanate (HDI), first poly(lactic acid) is carried out chain extending reaction and has been obtained success.Earlier with 1,4-butyleneglycol and lactic acid generate two lact-acid oligomers that end group all is a hydroxyl to Harkonen etc., carry out chain extending reaction with HDI again in preparation process, and the poly(lactic acid) relative molecular weight that obtains reaches 57000.
Domestic also have considerable scientific research institutions to be devoted to the work of PLA modification by copolymerization aspect at present.Tan (a state in the Zhou Dynasty) will waits has clearly invented the manufacture method that is used for absorbable medical suture PGA/PLA multipolymer, and this suture has favorable biological degradability, and intensity is higher, snappiness is good, extend moderate, nontoxicity, good biocompatibility, the absorption cycle is 60d～75d.Song Moudao has studied poly(lactic acid)/polyoxyethylene glycol (PEG) copolymerization process, and physics, the mechanical property of having tested multipolymer.Zhang Yanhong etc. adopt oligomeric D, and L-rac-Lactide and polycaprolactone oligopolymer have carried out chain extending reaction under 2,4 toluene diisocyanate (TDI) effect, have formed to have certain intensity and flexible elastomerics.Shen Zhengrong etc. have synthesized D, and L-3-methyl-glycollide, and be that catalyzer carries out ring-opening polymerization with stannous octoate has generated the alternating copolymer of PLA and PGA, this copolymer structure is regular, form fixingly, have improved the shortcoming that the PGA homopolymer is insoluble to common organic solvents.The Fan Changlie of Wuhan University etc. as slowly-releasing drug material and pharmaceutical carrier, because people's body includes phosphoric acid ester and poly phosphate, so this material has excellent biological compatibility, have also been given the character of similar crude substance with lactic acid and phosphoric acid ester copolymerization simultaneously.Though above-mentioned modification by copolymerization to poly(lactic acid) has been improved some performances of poly(lactic acid) to a certain extent, it is less to improve poly(lactic acid) flexible method.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of technology is simple, be easy to the good full biodegradation polyester copolymer of suitability for industrialized production, toughness.
The preparation method of the full biodegradation polyester copolymer that the present invention proposes, prepare the lactic acid pre-polymerization polycondensate of carboxy blocking by lactic acid and the direct fusion of small molecules diprotic acid, and then go out copolymer of poly lactic acid with aliphatic polycarbonate dibasic alcohol copolymerization, at last copolymer of poly lactic acid is carried out chain extension in twin screw extruder, obtain relative poly-lactic acid in high molecular weight base co-polymer.Its concrete steps are as follows:
(1) lactic acid is joined in the reactor, under 100～160 ℃ of temperature, carry out processed, then in reactor, add the small molecules diprotic acid, vacuumize, under catalyst action, carry out polycondensation, control reactor pressure is 1000～2000Pa, and temperature of reaction is 90～120 ℃, and the reaction times is 1～10 hour, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 150～200 ℃, continue reaction 5～20 hours, promptly obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer; Wherein, the mol ratio of lactic acid and small molecules diprotic acid is 50: 1～10: 1;
(2) carboxy blocking lactic acid prepolymer and the aliphatic polycarbonate dibasic alcohol that obtains in the step (1) joined in the reactor, vacuumize, at N
2Under the atmosphere, carry out polyreaction, temperature of reaction is 150～200 ℃, and the reaction times is 1～10 hour, promptly obtains the low molecular weight Copolycarbonate, its weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4Wherein, the mol ratio of carboxy blocking lactic acid prepolymer and aliphatic polycarbonate dibasic alcohol is 3: 1～1: 1;
(3) the low molecular weight Copolycarbonate that obtains in the step (2) is joined in the twin screw extruder, under catalyzer and chainextender effect, carry out chain extending reaction, the control screw speed is 10～100 rev/mins, extrusion temperature is 140～190 ℃, the residence time of material is 5～15 minutes, promptly obtains desired product.
Among the present invention, small molecules diprotic acid structural formula is as follows in the step (1):
Wherein n is 1～6 integer.
Among the present invention, described aliphatic polycarbonate dibasic alcohol is poly (propylene carbonate) glycol, poly-carbonic acid 1,6-hexylene glycol esterdiol, poly-carbonic acid 1,5-pentanediol-1,6-hexylene glycol ester, polyhexamethylene carbonic ether glycol or poly-carbonic acid 1, in the 4-butanediol ester glycol etc. any.
Among the present invention, described aliphatic polycarbonate dibasic alcohol weight-average molecular weight M
wBe 1000～5000.
Among the present invention, catalyzer described in step (1) and (3) is the one to multiple kind in stannous octoate, tin protochloride, dibutyltin dilaurate, antimonous oxide, germanium chloride, iron octoate, cobalt octoate, epoxyeicosatrienoic acid zinc, triethylenediamine, thanomin or the diethanolamine etc.; The add-on of catalyzer is 0.1～10wt% of lactic acid quality in the step (1), and the add-on of catalyzer is 0.1～10wt% of polylactic acid poly carbonate copolymer quality in the step (3).
Among the present invention, chainextender described in the step (3) be diisocyanate compound, isocyanate ester compound or amides etc. any, low molecular weight Copolycarbonate and chainextender mol ratio are 3: 1～1: 1.
Among the present invention, earlier the low molecular weight Copolycarbonate is made with extra care, purified before the chain extending reaction.
The invention has the advantages that:
(1) introducing aliphatic acid ester carbonate is soft segment, has changed the fragility of poly(lactic acid) itself, makes the multipolymer of preparing have good mechanical property.
(2) copolymerization product is a Biodegradable material, and environmentally safe can effectively solve " white pollution " problem.
(3) the present invention adopts twin screw production, and technology is simple, feasible, is easy to suitability for industrialized production.
Embodiment
Embodiment 1:
(1) with 400gL-lactic acid under 100 ℃, in reactor, carry out processed, add the 20g Succinic Acid then, vacuumize, under the inferior tin effect of 0.5g octoate catalyst, carry out polycondensation, pressure in the reactor is 1000Pa, and temperature is 90 ℃, reacts 10 hours, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 150 ℃, continue reaction 15 hours, obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer;
(2) carboxy blocking lactic acid prepolymer and the 200g poly (propylene carbonate) glycol (molecular weight 2000) that obtains in the step (1) joined in the reactor, vacuumize, logical N
2Gas carries out polyreaction; Temperature of reaction is 150 ℃, reacts 10 hours, promptly obtains the low molecular weight Copolycarbonate, this product weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4
(3) inferior tin of low molecular weight Copolycarbonate, octoate catalyst and the chainextender hexamethylene diisocyanate (HDI) that obtains in the step (2) carried out chain extending reaction in twin screw extruder, wherein low molecular weight Copolycarbonate and HDI molar weight ratio are 3: 1, the inferior tin add-on of octoate catalyst is 0.7g, screw speed is 100 rev/mins, extrusion temperature is 140 ℃, residence time of material is 5 minutes, obtain poly(lactic acid)/Copolycarbonate, this product weight-average molecular weight M
wBe 1 * 10
5～2 * 10
5
Embodiment 2:
(1) with 800gL-lactic acid under 110 ℃, in reactor, carry out processed, add the 40g Succinic Acid then, vacuumize, under the inferior tin effect of 1g octoate catalyst, carry out polycondensation, pressure in the reactor is 1500Pa, and temperature is 100 ℃, reacts 2 hours, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 160 ℃, continue reaction 10 hours, obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer;
(2) with the carboxy blocking lactic acid prepolymer and the poly-carbonic acid 1 of 300g that obtain in the step (1), 6-hexylene glycol esterdiol (molecular weight 3000) joins in the reactor, vacuumizes, logical N
2Gas carries out polyreaction; Temperature of reaction is 170 ℃, reacts 10 hours, promptly obtains the low molecular weight Copolycarbonate, this product weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4
(3) inferior tin of low molecular weight Copolycarbonate, octoate catalyst and the chainextender hexamethylene diisocyanate (HDI) that obtains in the step (2) carried out chain extending reaction in twin screw extruder, wherein low molecular weight Copolycarbonate and HDI molar weight ratio are 2: 1, the stannous octoate add-on is 2g, screw speed is 50 rev/mins, extrusion temperature is 150 ℃, residence time of material is 8 minutes, obtains poly(lactic acid)/Copolycarbonate, this product weight-average molecular weight M
wBe 1 * 10
5～2 * 10
5
Embodiment 3:
(1) with 600gL-lactic acid under 120 ℃, in reactor, carry out processed, add the 40g Succinic Acid then, vacuumize, under the inferior tin effect of 1g octoate catalyst, carry out polycondensation, pressure in the reactor is 1800Pa, and temperature is 120 ℃, reacts 3 hours, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 170 ℃, continue reaction 6 hours, obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer;
(2) with the carboxy blocking lactic acid prepolymer and the poly-carbonic acid 1 of 400g that obtain in the step (1), 5-pentanediol-1,6-hexylene glycol ester (molecular weight 4000) joins in the reactor, vacuumizes, logical N
2Gas carries out polyreaction; Temperature of reaction is 180 ℃, reacts 8 hours, promptly obtains the low molecular weight Copolycarbonate, this product weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4
(3) with the low molecular weight Copolycarbonate, catalyzer tin protochloride and the chainextender ditan-4 that obtain in the step (2), 4 '-vulcabond (MDI) carries out chain extending reaction in twin screw extruder, wherein low molecular weight Copolycarbonate and MDI molar weight ratio are 1: 1, the stannous octoate add-on is 3g, screw speed is 40 rev/mins, extrusion temperature is 160 ℃, residence time of material is 10 minutes, obtain poly(lactic acid)/Copolycarbonate, this product weight-average molecular weight M
wBe 1 * 10
5～2 * 10
5
Embodiment 4:
(1) with 200gL-lactic acid under 130 ℃, in reactor, carry out processed, add the 20g Succinic Acid then, vacuumize, under the effect of 0.5g catalyzer tin protochloride, carry out polycondensation, pressure in the reactor is 1900Pa, and temperature is 110 ℃, reacts 5 hours, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 180 ℃, continue reaction 6 hours, obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer;
(2) carboxy blocking lactic acid prepolymer and the 200g polyhexamethylene carbonic ether glycol (molecular weight 2000) that obtains in the step (1) joined in the reactor, vacuumize, logical N
2Gas carries out polyreaction; Temperature of reaction is 190 ℃, reacts 5 hours, promptly obtains the low molecular weight Copolycarbonate, this product weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4
(3) with the low molecular weight Copolycarbonate, catalyzer tin protochloride and the chainextender ditan-4 that obtain in the step (2), 4 '-vulcabond (MDI) carries out chain extending reaction in twin screw extruder, wherein low molecular weight Copolycarbonate and HDI molar weight ratio are 2: 1, the stannous octoate add-on is 5g, screw speed is 50 rev/mins, extrusion temperature is 170 ℃, residence time of material is 8 minutes, obtain poly(lactic acid)/Copolycarbonate, this product weight-average molecular weight M
wBe 1 * 10
5～2 * 10
5
Embodiment 5:
(1) with 500gL-lactic acid under 160 ℃, in reactor, carry out processed, add the 50g Succinic Acid then, vacuumize, under the effect of 3g catalyzer dibutyltin dilaurate, carry out polycondensation, pressure in the reactor is 2000Pa, and temperature is 120 ℃, reacts 1 hour, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 200 ℃, continue reaction 5 hours, obtain M
w=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer;
(2) with the carboxy blocking lactic acid prepolymer and the poly-carbonic acid 1 of 500g that obtain in the step (1), 4-butanediol ester glycol (molecular weight 4000) joins in the reactor, vacuumizes, logical N
2Gas carries out polyreaction; Temperature of reaction is 200 ℃, reacts 1 hour, promptly obtains the low molecular weight Copolycarbonate, this product weight-average molecular weight M
wBe 2 * 10
3～5 * 10
4
(3) with the low molecular weight Copolycarbonate, catalyzer tin protochloride and the chainextender ditan-4 that obtain in the step (2), 4 '-vulcabond (MDI) carries out chain extending reaction in twin screw extruder, wherein low molecular weight Copolycarbonate and MDI molar weight ratio are 3: 1, the stannous octoate add-on is 5g, screw speed is 10 rev/mins, extrusion temperature is 190 ℃, residence time of material is 15 minutes, obtain poly(lactic acid)/Copolycarbonate, this product weight-average molecular weight M
wBe 1 * 10
5～2 * 10
5
Claims (3)
1, a kind of preparation method of full biodegradation polyester copolymer is characterized in that concrete steps are as follows:
(1) lactic acid is joined in the reactor, under 100～160 ℃ of temperature, carry out processed, then in reactor, add the small molecules diprotic acid, vacuumize, under catalyst action, carry out polycondensation, control reactor pressure is 1000～2000Pa, and temperature of reaction is 90～120 ℃, and the reaction times is 1～10 hour, then the pressure in the reactor is reduced to below the 100Pa, temperature of reaction is risen to 150～200 ℃, continue reaction 5～20 hours, promptly obtain Mw=8 * 10
2～3.0 * 10
4The carboxy blocking lactic acid prepolymer; Wherein, the mol ratio of lactic acid and small molecules diprotic acid is 50: 1～10: 1;
(2) carboxy blocking lactic acid prepolymer and the aliphatic polycarbonate dibasic alcohol that obtains in the step (1) joined in the reactor, vacuumize, at N
2Under the atmosphere, carry out polyreaction, temperature of reaction is 150～200 ℃, and the reaction times is 1～10 hour, promptly obtains the low molecular weight Copolycarbonate, and its weight-average molecular weight Mw is 2 * 10
3～5 * 10
4Wherein, the mol ratio of carboxy blocking lactic acid prepolymer and aliphatic polycarbonate dibasic alcohol is 3: 1～1: 1;
(3) the low molecular weight Copolycarbonate that obtains in the step (2) is joined in the twin screw extruder, under catalyzer and chainextender effect, carry out chain extending reaction, the control screw speed is 10～100 rev/mins, extrusion temperature is 140～190 ℃, the residence time of material is 5～15 minutes, promptly obtains desired product;
Small molecules diprotic acid structural formula is as follows in the step (1):
Wherein n is 1～6 integer;
Described aliphatic polycarbonate dibasic alcohol weight-average molecular weight Mw is 1000～5000;
Catalyzer described in step (1) and (3) is the one to multiple kind in stannous octoate, tin protochloride, dibutyltin dilaurate, antimonous oxide, germanium chloride, iron octoate, cobalt octoate, epoxyeicosatrienoic acid zinc, triethylenediamine, thanomin or the diethanolamine; The add-on of catalyzer is 0.1～10wt% of lactic acid quality in the step (1), and the add-on of catalyzer is 0.1～10wt% of polylactic acid poly carbonate copolymer quality in the step (3);
Chainextender described in the step (3) be in diisocyanate compound, isocyanate ester compound or the amides any, low molecular weight Copolycarbonate and chainextender mol ratio are 3: 1～1: 1.
2, the preparation method of full biodegradation polyester copolymer according to claim 1, it is characterized in that described aliphatic polycarbonate dibasic alcohol is poly (propylene carbonate) glycol, poly-carbonic acid 1,6-hexylene glycol esterdiol, poly-carbonic acid 1,5-pentanediol-1,6-hexylene glycol ester, polyhexamethylene carbonic ether glycol or poly-carbonic acid 1, in the 4-butanediol ester glycol any.
3, the preparation method of full biodegradation polyester copolymer according to claim 1 is characterized in that earlier the low molecular weight Copolycarbonate being made with extra care, being purified before the chain extending reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100445077A CN100558787C (en) | 2007-08-02 | 2007-08-02 | A kind of preparation method of full biodegradation polyester copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100445077A CN100558787C (en) | 2007-08-02 | 2007-08-02 | A kind of preparation method of full biodegradation polyester copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101121781A CN101121781A (en) | 2008-02-13 |
| CN100558787C true CN100558787C (en) | 2009-11-11 |
Family
ID=39084295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100445077A Active CN100558787C (en) | 2007-08-02 | 2007-08-02 | A kind of preparation method of full biodegradation polyester copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100558787C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245178B (en) * | 2008-03-06 | 2010-12-01 | 同济大学 | Method for manufacturing biologically degradable polyester composite material with capacity increasing function |
| CN101962470B (en) * | 2009-07-22 | 2012-12-26 | 中国海洋石油总公司 | Biodegradable polypropylene carbonate composite material and preparation method thereof |
| CN102358778B (en) * | 2011-07-29 | 2014-06-18 | 上海载和实业投资有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN102516733B (en) * | 2011-12-02 | 2013-07-31 | 宁波锦海模具塑膠有限公司 | Polycarbonate alloy material containing biology-based high polymer and preparation method thereof |
| CN105175676B (en) * | 2015-10-14 | 2018-01-02 | 中国科学院宁波材料技术与工程研究所 | Medical infusion apparatus PLA based polyurethanes elastomeric material and preparation method thereof |
| CN105315416B (en) * | 2015-12-02 | 2018-02-23 | 河北麦格尼菲复合材料股份有限公司 | Recyclable organism-based vinyl ester resin and preparation method thereof |
| CN108314769A (en) * | 2017-01-16 | 2018-07-24 | 中国科学院宁波材料技术与工程研究所 | A kind of reactive extrursion prepares the method and its application of polylactic acid based polyurethanes elastomer |
| CN110283326A (en) * | 2018-12-12 | 2019-09-27 | 杭州师范大学 | A kind of degradable modification poly (propylene carbonate) and preparation method thereof |
| CN110527304A (en) * | 2019-09-16 | 2019-12-03 | 湖南七纬科技有限公司 | A kind of degradable plastic glue material and preparation method thereof |
| CN115103830A (en) * | 2019-12-19 | 2022-09-23 | 伊士曼化工公司 | Method for producing dimethyl terephthalate by polyester methanol decomposition depolymerization system |
| CN112920388B (en) * | 2021-01-27 | 2022-10-21 | 江苏睿安应用生物技术股份有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
| CN113527627A (en) * | 2021-08-18 | 2021-10-22 | 中国科学院海洋研究所 | Polylactic acid polycarbonate-based polyurethane with self-repairing function and preparation method and application thereof |
| CN115232315B (en) * | 2022-06-30 | 2023-06-13 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate multiblock copolymer and preparation method thereof |
| CN115232297B (en) * | 2022-06-30 | 2023-06-27 | 中国神华煤制油化工有限公司 | Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof |
| CN115558478B (en) * | 2022-11-07 | 2023-06-30 | 四川捷贝通能源科技有限公司 | Preparation method of high-strength full-degradable bionic temporary plugging material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546549A (en) * | 2003-12-04 | 2004-11-17 | 中国科学院上海有机化学研究所 | Bio-degradability polyester block macromolecule copolymer, preparation method and uses |
| CN1563139A (en) * | 2004-03-25 | 2005-01-12 | 同济大学 | Direct fusion method for preparing poly lactic acid in high molecular weight |
| CN1908030A (en) * | 2006-08-10 | 2007-02-07 | 同济大学 | Preparation method of full biodegradation polyester copolymer |
| CN1908031A (en) * | 2006-08-10 | 2007-02-07 | 同济大学 | Method of preparing full biodegradation copolymer from ring-opening polymer |
| CN1927911A (en) * | 2006-09-07 | 2007-03-14 | 同济大学 | Preparation method of biodegradation polylactic acid based multicomponent block polymer |
-
2007
- 2007-08-02 CN CNB2007100445077A patent/CN100558787C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546549A (en) * | 2003-12-04 | 2004-11-17 | 中国科学院上海有机化学研究所 | Bio-degradability polyester block macromolecule copolymer, preparation method and uses |
| CN1563139A (en) * | 2004-03-25 | 2005-01-12 | 同济大学 | Direct fusion method for preparing poly lactic acid in high molecular weight |
| CN1908030A (en) * | 2006-08-10 | 2007-02-07 | 同济大学 | Preparation method of full biodegradation polyester copolymer |
| CN1908031A (en) * | 2006-08-10 | 2007-02-07 | 同济大学 | Method of preparing full biodegradation copolymer from ring-opening polymer |
| CN1927911A (en) * | 2006-09-07 | 2007-03-14 | 同济大学 | Preparation method of biodegradation polylactic acid based multicomponent block polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101121781A (en) | 2008-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100558787C (en) | A kind of preparation method of full biodegradation polyester copolymer | |
| CN100558786C (en) | A kind of preparation method of polylactic acid group block copolymer | |
| Valderrama et al. | The potential of oxalic–and glycolic acid based polyesters (review). Towards CO2 as a feedstock (Carbon Capture and Utilization–CCU) | |
| CN100558795C (en) | The preparation method of biodegradation polylactic acid based multicomponent block polymer | |
| CN100535033C (en) | Polylactic-acid block copolymer and preparation method thereof | |
| CN101899139B (en) | Method for preparing polylactic acid-based high-elasticity copolymer | |
| CN100523050C (en) | Method for preparing polylactic acid-polycarbonate copolymers | |
| CN111087580B (en) | Process for preparing polyglycolic acid | |
| CN100406498C (en) | Blend material of vinol/polylactic acid graft copolymer and starch, their prepn. and application | |
| Quattrosoldi et al. | Fully biobased, elastomeric and compostable random copolyesters of poly (butylene succinate) containing Pripol 1009 moieties: Structure-property relationship | |
| CN100445313C (en) | Method for preparing polylactic acid/polyether divalent alcohol copolymers | |
| Hong et al. | Synthesis and characterization of biodegradable poly (ɛ-caprolactone-co-β-butyrolactone)-based polyurethane | |
| CN102604052B (en) | Method for preparing poly(2-methyl butylene succinate) with high molecular weight (HMW) | |
| JP2006183042A (en) | New multiblock copolymer, method for producing the same, and its utilization | |
| CN105273185A (en) | Method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through nonisocyanate method | |
| CN101096415B (en) | Poly(P-dioxanone) and preparation method thereof | |
| CN102702491A (en) | Multi-arm polylactic acid composition and preparation method thereof | |
| CN106397721B (en) | A kind of preparation method of the Biodegradable polyurethane containing unsaturated bond | |
| CN111892703B (en) | Biodegradable thermoplastic polyester elastic material and preparation method thereof | |
| CN112194781A (en) | Method for preparing polyester polyol from glycolic acid | |
| CN103073709B (en) | A kind of preparation method of poly-2-dimethyl succinic acid DOPCP | |
| JP2006152196A (en) | Biodegradable resin composition | |
| CN117069924A (en) | Full-bio-based polylactic acid copolyol and synthetic method thereof | |
| KR100817905B1 (en) | Biodegradable aliphatic polyester resin compositionand preparation thereof on the excellence of bionics adapt | |
| Jing et al. | Biocompatible polyurethanes with thermally-induced shape memory properties derived from three-arm branched poly (ε-caprolactone-co-γ-butyrolactone)-b-poly (lactide) block copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |