CN106957412A - It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer - Google Patents
It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer Download PDFInfo
- Publication number
- CN106957412A CN106957412A CN201710186878.2A CN201710186878A CN106957412A CN 106957412 A CN106957412 A CN 106957412A CN 201710186878 A CN201710186878 A CN 201710186878A CN 106957412 A CN106957412 A CN 106957412A
- Authority
- CN
- China
- Prior art keywords
- glycolide
- random copolymer
- caprolactone
- preparation
- biodegradable 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Present invention is disclosed a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer, comprises the following steps：The glycolide of different proportion and ε caprolactones monomer are mixed and added in pressure reaction still, octoate catalyst stannous is added, under protective gas atmosphere; in being reacted under uniform temperature and mixing speed after a period of time, temperature drops to room temperature, discharge degree to atmospheric pressure; terminating reaction, is gathered（Glycolide ε caprolactones）Random copolymer.The present invention is gathered under protective gas atmosphere hyperbaric environment（Glycolide ε caprolactones）The preparation of random copolymer, it is to avoid vacuum condition prepared by conventional polyester class homopolymer or copolymer, reduces the equipment cost of production, more conducively large-scale industrial production；The ring-opening polymerization that ring-opening polymerization under protective gas atmosphere is compared under vacuum condition is more beneficial for the radiating of course of reaction, makes polymerisation evenly.
Description
Technical field
The invention belongs to field of biomedical polymer materials, it is related to a kind of biodegradable poly-（Glycolide-ε-caprolactone）
The preparation method of random copolymer.
Background technology
The Biodegradable high moleculars such as polylactide and its copolymer have obtained more and more wider in medicine equipment and pharmaceutic adjuvant
General application.In terms of medicine equipment, the medical device product such as operation suture thread, blood vessel clip, sticking patch, stapler, nail, hone lamella
The country is currently under the critical period from non-biodegradable material to biodegradated polymer materal transition and popularization and application；
In terms of pharmaceutic adjuvant, the muscle such as medicament carrier microspheres and micella of biodegradated polymer materal and intravenous injection medicine
A large amount of to carry out clinical test, some products are in the multiple national list marketings in west.Medical biodegradable macromolecule material
Material is to ratify to can be used for the material of human body through FDA, and its internal security has sufficient guarantee.Biodegradable medical device product
The characteristics of be that product category is more, broad covered area, product is related to that chest is outer, abdomen is outer, brain is outer, ear nose larynx, uropoiesis, gynaecology, angiocarpy etc.
Almost all of section office.Therefore, its diversity to biodegradated polymer materal proposes strict requirements.With PLA and
Biodegradated polymer materal based on its copolymer has obtained large-scale popularization in implanted medical device product, such as poly-
（Lactic acid-ethanol）Copolymer p LGA10/90 occupies the market share of most synthesising biological degraded operation suture thread.
It is poly-（Lactide coglycolide）Copolymer is due to its higher glass transition temperature（50-60℃）, make it at room temperature
The poor flexibility used, is subject to certain restrictions as medical device product during use.It is poly-（ε-caprolactone）Glass
Change transition temperature low（- 60 DEG C or so）, the copolymer of ε-caprolactone and lactide can reduce the glass transition temperature of PLA
Degree, improves the elasticity and elongation at break of this kind of Biodegradable high molecular.Due to the superpower crystal property of PGA, when poly- second
The molecular weight of lactide homopolymer segment will produce the crystallization of PGA more than 1000, and it is different that PGA crystal is dissolved only in hexafluoro
The organic solvent of few species such as propyl alcohol, this is a very big problem to its processing and forming, and therefore, that reports at present is most of
In copolymer containing PGA, the molar content of PGA is below 50%, if content is higher than 50%, just easily produces
The crystallization of PGA, it is difficult to carry out the follow-up processing and forming of material.
Using glycolide and ε-caprolactone as keyword retrieval Chinese invention patent, it is found that the copolymer of PGA is mainly
It is poly-（Lactide coglycolide）Copolymer, does not almost gather（Glycolide-ε-caprolactone）The patent of synthetic method.Chinese patent（It is public
The number of opening CN105801817A）There is provided a kind of lactide and the copolymerization process of 6-caprolactone, two kinds are carried out with salen Al catalysts
The copolyreaction of monomer, this copolymerization process make it that the coordination of two kinds of monomers of lactide and 6-caprolactone is inserted speed and matched very much,
Very controllable random copolymerization can be realized.Chinese patent（Publication number CN104066459A）Disclose for can Long-term absorption medical science
New hypocrystalline, the 6-caprolactone rich in 6-caprolactone and the block copolymer to dioxanone of application.Novel polymeric
Compositions can be used for can Long-term absorption surgical sutures and other medical treatment devices.Chinese patent（Publication number
CN102532494A）Disclose a class lactide/6-caprolactone catalyst for copolymerization and copolymerization process.It is nitrogenous that catalyst is related to a class
Bis-phenol epoxide double-core aluminium complex.The described efficient lactide/6-caprolactone catalyst for copolymerization of this invention, can be achieved to include the third friendship
Ester/6-caprolactone block copolymer, gradient copolymer, the synthesis of wedge-shaped copolymer and random copolymer.Chinese patent（Publication number
CN105885021A）A kind of synthetic method of PGA homopolymer is disclosed, obtained PGA performance is homogeneous, can realize
Mass production, conversion ratio is higher.Chinese patent（Publication number CN102643411A）Disclose a kind of microwave irradiation synthesis microwave
The method of irradiation synthesis PGA and PLA-glycolide copolymer, its benefit is microwave radiation method synthesis PGA
Or PLA-glycolide copolymer reaction time is short, energy consumption is reduced, heat transfer is uniform, and monomer reaction is homogeneous.Chinese patent（It is open
Number CN101343354B）Disclose a kind of polylactide, PGA and should the two copolymer preparation method, by lactide or
Any one in three kinds of materials of mixture of glycolide or lactide and glycolide is considered as monomer, adds in the monomer and suspends
Agent, catalyst, then stir, heat up, aggregate into pelletized product.Above-mentioned patent is although the copolymerization of report ε-caprolactone or glycolide
The preparation method of thing, but be not poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer.
The content of the invention
Gathered it is an object of the invention to provide one kind under protective gas atmosphere hyperbaric environment（Glycolide-ε-
Lactone）The preparation of random copolymer, it is to avoid vacuum condition prepared by conventional polyester class homopolymer or copolymer, reduces production
Equipment cost, more conducively large-scale industrial production；Ring-opening polymerization under protective gas atmosphere compares vacuum condition
Under ring-opening polymerization be more beneficial for the radiating of course of reaction, gather the biodegradation of polymerisation evenly（Glycolide-ε-
Caprolactone）The preparation method of random copolymer.
The technical scheme is that, it is a kind of biodegradable poly-（Glycolide-ε-caprolactone）The preparation side of random copolymer
Method, comprises the following steps：The glycolide of different proportion and ε-caprolactone monomer are mixed and added in pressure reaction still, catalysis is added
Agent stannous octoate, under protective gas atmosphere, in being reacted under uniform temperature and mixing speed after a period of time, temperature drops to room
Temperature, discharge degree to atmospheric pressure, terminating reaction is gathered（Glycolide-ε-caprolactone）Random copolymer.
In a preferred embodiment of the present invention, the molar content of the glycolide is 30-90%.
In a preferred embodiment of the present invention, the percentage by weight of the octoate catalyst stannous is total monomer weight
0.01-5‰。
In a preferred embodiment of the present invention, the pressure of the protective gas is 0.1-10MPa.
In a preferred embodiment of the present invention, the protective gas is inert gas, specially in argon gas or nitrogen
At least one.
In a preferred embodiment of the present invention, reaction temperature is 100-220 DEG C.
In a preferred embodiment of the present invention, the protective gas of course of reaction is that inert gas includes argon gas or nitrogen
In at least one, the mixing speed be 10-200 revs/min.
In a preferred embodiment of the present invention, the time of reaction is 0.5-72 hours.
It is of the present invention to gather for a kind of biodegradation（Glycolide-ε-caprolactone）The preparation method of random copolymer, this hair
It is bright to be gathered under protective gas atmosphere hyperbaric environment（Glycolide-ε-caprolactone）The preparation of random copolymer, it is to avoid pass
Vacuum condition prepared by system polyesters homopolymer or copolymer, reduces the equipment cost of production, more conducively heavy industrialization
Production；The ring-opening polymerization that ring-opening polymerization under protective gas atmosphere is compared under vacuum condition is more beneficial for reacting
The radiating of journey, makes polymerisation evenly.
Brief description of the drawings
Fig. 1 is a kind of biodegradable poly- for the present invention（Glycolide-ε-caprolactone）The preparation method one of random copolymer is preferable
Differential scanning calorimeter in embodiment（DSC）Collection of illustrative plates；
Fig. 2 is a kind of biodegradable poly- for the present invention（Glycolide-ε-caprolactone）The preparation method one of random copolymer is preferably implemented
Fourier transform infrared in example（FTIR）Collection of illustrative plates.
Embodiment
Presently preferred embodiments of the present invention is described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that apparent clearly being defined so as to be made to protection scope of the present invention.
It is of the present invention to gather for a kind of biodegradation（Glycolide-ε-caprolactone）The preparation method of random copolymer, specifically
Step includes：The glycolide of different proportion and ε-caprolactone monomer are mixed（The molar content of glycolide is 30-90%）Add pressure
In power reactor, the octoate catalyst stannous that content is total monomer gross weight 0.01-5 ‰ is added, in the guarantor of 0.1-10MPa pressure
It is warm after being reacted 0.5-72 hour at a temperature of 100-220 DEG C, under 10-200 revs/min of mixing speed under shield property gas atmosphere
Degree drops to room temperature, and discharge degree to atmospheric pressure, terminating reaction is gathered（Glycolide-ε-caprolactone）Random copolymer.
Embodiment 1
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 90%）Add in pressure reaction still, addition contains
Measure the octoate catalyst stannous for total monomer gross weight 0.01 ‰, 10MPa pressure argon gas protection under, at 100 DEG C, 200
Rev/min mixing speed under reaction 72 hours after, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Glycolide-
ε-caprolactone）Random copolymer.
Embodiment 2
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 30%）Add in pressure reaction still, addition contains
Measure the octoate catalyst stannous for total monomer gross weight 5 ‰, 0.1MPa pressure nitrogen protection under, at 220 DEG C, 10 turns/
After being reacted 0.5 hour under the mixing speed of minute, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Glycolide-ε-
Caprolactone）Random copolymer.
Embodiment 3
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 75%）Add in pressure reaction still, addition contains
Measure the octoate catalyst stannous for total monomer gross weight 1 ‰, 0.5MPa pressure argon gas protection under, at 190 DEG C, 50 turns/
After being reacted 48 hours under the mixing speed of minute, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Glycolide-ε-
Lactone）Random copolymer.
Embodiment 4
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 50%）Add in pressure reaction still, addition contains
Measure the octoate catalyst stannous for total monomer gross weight 0.1 ‰, 5MPa pressure nitrogen protection under, at 150 DEG C, 120 turns/
After being reacted 60 hours under the mixing speed of minute, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Glycolide-ε-
Lactone）Random copolymer.
Embodiment 5
As depicted in figs. 1 and 2, glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 70%）Add pressure
In reactor, the octoate catalyst stannous that content is total monomer gross weight 0.5 ‰ is added, under the argon gas protection of 3MPa pressure,
After being reacted 36 hours at a temperature of 130 DEG C, under 60 revs/min of mixing speed, temperature drops to room temperature, discharge degree to air
Pressure, is gathered（Glycolide-ε-caprolactone）Random copolymer.
Embodiment 6
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 40%）Add in pressure reaction still, addition contains
The octoate catalyst stannous for total monomer gross weight 0.05 ‰ is measured, under the nitrogen protection of 0.8MPa pressure, in 175 DEG C of temperature
Under, under 150 revs/min of mixing speed react 30 hours after, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Second
Lactide-ε-caprolactone）Random copolymer.
Embodiment 7
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 80%）Add in pressure reaction still, addition contains
The octoate catalyst stannous for total monomer gross weight 0.3 ‰ is measured, under the argon gas protection of 0.2MPa pressure, at a temperature of 200 DEG C,
After being reacted 12 hours under 40 revs/min of mixing speed, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Second is handed over
Ester-ε-caprolactone）Random copolymer.
Embodiment 8
Glycolide and ε-caprolactone monomer are mixed（The molar content of glycolide is 30%）Add in pressure reaction still, addition contains
The octoate catalyst stannous for total monomer gross weight 1 ‰ is measured, under the nitrogen protection of 0.8MPa pressure, at a temperature of 110 DEG C,
After being reacted 72 hours under 100 revs/min of mixing speed, temperature drops to room temperature, and discharge degree is gathered to atmospheric pressure（Second is handed over
Ester-ε-caprolactone）Random copolymer.
It is of the present invention to gather for a kind of biodegradation（Glycolide-ε-caprolactone）The preparation method of random copolymer, this hair
It is bright to be gathered under protective gas atmosphere hyperbaric environment（Glycolide-ε-caprolactone）The preparation of random copolymer, it is to avoid pass
Vacuum condition prepared by system polyesters homopolymer or copolymer, reduces the equipment cost of production, more conducively heavy industrialization
Production；The ring-opening polymerization that ring-opening polymerization under protective gas atmosphere is compared under vacuum condition is more beneficial for reacting
The radiating of journey, makes polymerisation evenly.
The embodiment of the present invention is the foregoing is only, but protection scope of the present invention is not limited thereto, it is any
Those of ordinary skill in the art disclosed herein technical scope in, the change that can expect without creative work or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is defined.
Claims (8)
1. it is a kind of biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is characterised in that：Including as follows
Step：The glycolide of different proportion and ε-caprolactone monomer are mixed and added in pressure reaction still, octoate catalyst stannous is added,
Under protective gas atmosphere, in being reacted under uniform temperature and mixing speed after a period of time, temperature drops to room temperature, discharge degree
To atmospheric pressure, terminating reaction is gathered（Glycolide-ε-caprolactone）Random copolymer.
2. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The molar content of the glycolide is 30-90%.
3. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The percentage by weight of the octoate catalyst stannous is the 0.01-5 ‰ of total monomer weight.
4. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The pressure of the protective gas is 0.1-10MPa.
5. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The protective gas is inert gas, the specially at least one in argon gas or nitrogen.
6. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：Reaction temperature is 100-220 DEG C.
7. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The protective gas of course of reaction is that inert gas includes at least one in argon gas or nitrogen, the mixing speed
For 10-200 revs/min.
8. it is according to claim 1 biodegradable poly-（Glycolide-ε-caprolactone）The preparation method of random copolymer, it is special
Levy and be：The time of reaction is 0.5-72 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710186878.2A CN106957412A (en) | 2017-03-27 | 2017-03-27 | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710186878.2A CN106957412A (en) | 2017-03-27 | 2017-03-27 | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106957412A true CN106957412A (en) | 2017-07-18 |
Family
ID=59470371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710186878.2A Pending CN106957412A (en) | 2017-03-27 | 2017-03-27 | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106957412A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028655A (en) * | 2019-04-19 | 2019-07-19 | 杭州华威医疗用品有限公司 | Polyglycolide caprolactone copolymer ultrasonic synthetic method |
| WO2023076999A1 (en) | 2021-10-28 | 2023-05-04 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyester copolymer, preparation and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153071A (en) * | 2007-09-30 | 2008-04-02 | 大连海事大学 | Method of producing biological degradable aliphatic polyester for medical purpose |
| CN104558542A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Transparent elastic polylactic acid polymer and preparation method thereof |
-
2017
- 2017-03-27 CN CN201710186878.2A patent/CN106957412A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153071A (en) * | 2007-09-30 | 2008-04-02 | 大连海事大学 | Method of producing biological degradable aliphatic polyester for medical purpose |
| CN104558542A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Transparent elastic polylactic acid polymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张涵等: "聚（ε-己内酯-L-丙交酯）无规共聚物与聚乳酸共混材料的制备与性能", 《应用化学》 * |
| 白宝平等: "乙交酯-己内酯无规共聚物的合成及其降解性能", 《合成化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028655A (en) * | 2019-04-19 | 2019-07-19 | 杭州华威医疗用品有限公司 | Polyglycolide caprolactone copolymer ultrasonic synthetic method |
| WO2023076999A1 (en) | 2021-10-28 | 2023-05-04 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyester copolymer, preparation and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Poly (p-dioxanone) and its copolymers | |
| CN108250415B (en) | Poly (gamma-butyrolactone) -b-polylactic acid block copolymer and preparation method thereof | |
| CN104448261B (en) | High performance polymer amount poly (l-lactic acid) synthesis technique | |
| Jahandideh et al. | Star-shaped lactic acid based systems and their thermosetting resins; synthesis, characterization, potential opportunities and drawbacks | |
| CN105131259B (en) | Biological guanidine compound system catalytic fusion solid phase synthesizes high-molecular-weight poly alpha-hydroxy acid | |
| WO2021243870A1 (en) | Ring opening polymerization method for cyclic monomer | |
| CN106957412A (en) | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer | |
| CN101353420B (en) | Solvent-thermal synthesis preparation of polylactic acid-polyethyleneglycol copolymer | |
| CN101864061A (en) | Microwave irradiation method for preparing star polycaprolactone-polylactic acid block copolymer | |
| CN101134808A (en) | Method for catalyzing polymerization of cyclic lactone | |
| CN105348495A (en) | Catalyst for polylactone preparation | |
| CN107556465A (en) | Zinc coordination polymer and preparation method with catalyzing ring-opening polymerization of lactide performance | |
| CN1234750C (en) | Technological method of catalytic synthesizing medical biodegradable material with biomass organic guanidine compound | |
| CN102643411A (en) | Method for synthesizing polyglycolide and polylactic acid-glycolide copolymer by microwave irradiation | |
| CN106986984A (en) | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of block copolymer | |
| US8242186B2 (en) | Lactic acid oligomer and method for producing the same | |
| CN108559067A (en) | Long-chain branched polymer type processing aid and preparation method thereof and its application | |
| CN111087596B (en) | Method for preparing polyglycolide by continuous ring opening, catalyst and preparation method | |
| CN102295765A (en) | Copolycondensation synthesized polylactic acid-glycollic acid catalyzed by biomass creatinine | |
| CN109970954A (en) | Controllable biodegradable copolymer material and preparation method thereof and its application | |
| CN110396189A (en) | A kind of method of organic catalysis synthesis of polyester amide material | |
| CN107540824B (en) | Macromole evocating agent and condensation-open loop-solid phase combination synthesis superelevation isotacticity poly- L-/D- lactic acid method | |
| CN102702488A (en) | Preparation method for polylactic acid | |
| CN113999401B (en) | Cobalt-containing isopolymolybdic acid metal organic framework material and preparation method and application thereof | |
| CN102702491A (en) | Multi-arm polylactic acid composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170718 |
|
| RJ01 | Rejection of invention patent application after publication |