CN105384919A - Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide - Google Patents
Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide Download PDFInfo
- Publication number
- CN105384919A CN105384919A CN201510922282.5A CN201510922282A CN105384919A CN 105384919 A CN105384919 A CN 105384919A CN 201510922282 A CN201510922282 A CN 201510922282A CN 105384919 A CN105384919 A CN 105384919A
- Authority
- CN
- China
- Prior art keywords
- polyester
- fluoroform sulfimide
- reaction
- lactide
- prepare
- 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
- 0 CC(CCNS(C(F)(F)F)(=*)=O)CCS(C(F)(F)F)(*=O)=O Chemical compound CC(CCNS(C(F)(F)F)(=*)=O)CCS(C(F)(F)F)(*=O)=O 0.000 description 2
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
- C08G63/78—Preparation processes
-
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
Abstract
The invention discloses a method for preparing polyester through ring-opening polymerization, and belongs to the technical field of polymer material synthesis. The method comprises the following steps: carrying out a bulk polymerization reaction on cyclic ester as a reaction monomer by using bis(trifluoromethylsulfonyl)imide as a catalyst and organic alcohol ROH as an initiator, and separating obtained products to obtain the polyester. The method for preparing the polyester, provided by the invention, has the advantages of simplicity, low cost, high reaction rate, fast reaction, controllable process, mild reaction conditions and narrow molecular weight distribution.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, refer to that two fluoroform sulfimide salt catalyzed ring opening polymerization prepares the method for polyester.
Background technology
The ring-opening polymerization of cyclic ester is considered to one of the most controlled method of synthetic fat adoption ester, and the polymkeric substance using this method to synthesize has the controlled and feature that molecular weight distribution is narrower of molecular weight.Utilize different catalysis/initiator system, Biodegradable polyester is prepared in the ring-opening polymerization realizing cyclic ester, is the important channel of environmentally friendly polymkeric substance development.Biodegradable polyester has the characteristics such as capable of circulation, degradable, not only can solve the white pollution problems of plastic applications, and compare with environment negative impact greatly with the consumed resource of traditional industry macromolecular material, it is while boosting economic growth, water, the energy and raw-material consumption can be saved, reduce waste discharge simultaneously.This kind polyester, because of the ester bond containing facile hydrolysis in polymkeric substance, easily progressively resolves into oligopolymer or monomer, changes into carbonic acid gas and water further subsequently under microbial process, can show certain biocompatibility.This all has huge applications potentiality in the field such as biological medicine, organizational project.
Ten years in the past, the research utilizing metallic compound to prepare polyester is also a lot.Utilize metallic zinc mixture (J.Am.Chem.Soc.2003,125,11350-11359; J.Am.Chem.Soc.2001,123,3229-3238), metallic aluminium mixture (J.Am.Chem.Soc.2003,125,11291-11298) rare-earth metal complex (Angew.Chem.2006,118,2848-2850) prepare polylactide, although these paradigmatic systems have very high activity, but these catalysis systems are extremely sensitive to empty G&W, and are not suitable for suitability for industrialized production.In numerous metal composite, calcium metal mixture is more by the favor of investigator, because calcium metal is cheap and nontoxic.Use the ring-opening polymerization of the complex-catalyzed rac-Lactide of tetrahydrochysene lime borate in (Chem.Commun.2011,47,2276-2278), the preparation process of catalyzer is more complicated, also needs subzero treatment.
In this patent, we adopt two fluoroform sulfimide salt to carry out catalysis cyclic esters ring-opening polymerization as catalyzer.Two fluoroform sulfimide salt is that one has fine deliquescent material in water and methyl alcohol, so in the process obtaining polymkeric substance, there will not be the phenomenon of catalyst residue.And body series adopts the mode of mass polymerization, do not need to use extra solvent in reaction system, convenient suitability for industrialized production, in mass polymerization system, the higher temperature of general employing is reacted, and the susceptibility of reaction system to empty G&W is reduced greatly.
Summary of the invention
The invention provides a kind of simple process, with low cost, the efficient method of speed of reaction prepares polyester, the method has reaction fast, process control, and reaction conditions is gentle, the advantage of narrow molecular weight distribution.
Technical scheme of the present invention
The method of polyester is prepared in the ring-opening polymerization of provided by the invention pair of fluoroform sulfimide salt catalysis, utilize cyclic ester as reaction monomers, two fluoroform sulfimide salt, as catalyzer, utilizes organic alcohol roh as initiator, carry out bulk polymerization, be isolated to polyester.
The lactone described in method more than preparing polyester is butyrolactone, valerolactone, caprolactone; Carbonic ether is trimethylene carbonate, dimethyl carbonate, diethyl carbonate; Lactide is glycollide, rac-Lactide.Wherein lactone δ-valerolactone, 6-caprolactone; Carbonic ether is trimethylene carbonate; Lactide is L-rac-Lactide.Optimum lactone δ-valerolactone, 6-caprolactone; Carbonic ether is trimethylene carbonate; Lactide is L-rac-Lactide.
Described two fluoroform sulfimide salt are two fluoroform sulfimide calcium, two fluoroform sulfimide magnesium, two fluoroform sulfimide lithium, two fluoroform sulfimide aluminium, two fluoroform sulfimide zinc, two fluoroform sulfimide copper, two fluoroform sulfimide sodium, two fluoroform sulfimide potassium.Optimum is two fluoroform sulfimide calcium.
Described organic alcohol roh, wherein R is alkyl or phenyl.Described alkyl is have the straight chain of 1 to 22 carbon atom, side chain or closed chain.Described Organic Alcohol is methyl alcohol, ethanol, tetramethylolmethane, butynol, phenylpropyl alcohol, phenylcarbinol.Optimum Organic Alcohol is phenylcarbinol.
Described method temperature of reaction is 40 ~ 120 DEG C, and the reaction times is 1 ~ 24 hour, and the mol ratio of described monomer, two fluoroform sulfimide salt, Organic Alcohol is (30: 1: 1) ~ (200: 1: 1).
More than prepare in the method for polyester, the general structure of described monomer L-rac-Lactide is:
The general structure of described monomer trimethylene carbonate is:
The general structure of described monomer δ-valerolactone is:
The general structure of described monomer 6-caprolactone is:
The general structure of the calcium salt of described two fluoroform sulfimides is:
The general structure of described PLLA is:
The general structure of described PTMC is:
The general structure of described poly-valerolactone is:
The general structure of described polycaprolactone is:
Wherein n, m, x, y represent the different polymerization degree respectively, such as: if the rac-Lactide of the reaction in the monomer fed intake is 1, then n=1, if the rac-Lactide of the reaction in the monomer fed intake is 2, then n=2 is by that analogy.M, x, y are also like this.
In the preparation method of polyester, the structure of polymkeric substance is by the qualification of hydrogen spectrum, and molecular weight and the dispersity character of polymkeric substance are measured by size exclusion chromatography.
In the preparation method of PLLA, comprising the mol ratio of monomer L-rac-Lactide, two fluoroform sulfimide calcium, phenylcarbinol is (30: 1: 1) ~ (200: 1: 1).Temperature of reaction is for being 120 DEG C, and the reaction times is 1 ~ 24 hour.After reaction terminates, obtain polylactide.
In the preparation method of PTMC, comprising the mol ratio of monomer trimethylene carbonate, two fluoroform sulfimide calcium, phenylcarbinol is (30: 1: 1) ~ (200: 1: 1).The bulk reaction temperature of PTMC is 60 DEG C, and the reaction times is 1 ~ 24 hour.After reaction terminates, obtain PTMC.
In the preparation method of poly-valerolactone, comprising the mol ratio of monomer δ-valerolactone, two fluoroform sulfimide calcium, phenylcarbinol is (30: 1: 1) ~ (200: 1: 1).The bulk reaction temperature of poly-valerolactone is 120 DEG C, and the reaction times is 1 ~ 24 hour.After reaction terminates, obtain poly-valerolactone.
In the preparation method of polycaprolactone, comprising the mol ratio of monomer 6-caprolactone, two fluoroform sulfimide calcium, phenylcarbinol is (30: 1: 1) ~ (200: 1: 1).The bulk reaction temperature of polycaprolactone is 120 DEG C, and the reaction times is 1 ~ 24 hour.After reaction terminates, obtain polycaprolactone.
Beneficial effect of the present invention
1, two fluoroform sulfimide calcium treating system is adopted, compared to its metal residuals brought of metal catalyst such as organic tin salt, organic zinc salt and organic aluminium salts, determine to be solved preferably to cytotoxicity is large etc., synthesized polyester has higher biological safety, can have good application in medical material field.
2, this technique can according to demand, the product polyester of controlled synthesis target molecular weight, and product yield is high, and monomer-free remains, and color and luster is snow-white.
3, adopt the polymerization methods of mass polymerization, do not need in reaction system to add extra solvent, facilitate suitability for industrialized production.
Accompanying drawing explanation
Fig. 1. the preparation method of PLLA
Fig. 2. the preparation method of PTMC
Fig. 3. the hydrogen spectrogram of polylactide
Fig. 4. the hydrogen spectrogram of PTMC
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not restricted to this.Lactide with L-rac-Lactide for embodiment; Carbonic ether with trimethylene carbonic ether for embodiment; Lactone is with δ-valerolactone, and 6-caprolactone is embodiment.
Embodiment 1
In the polymerizing pipe of 10ml, add L-rac-Lactide (0.432g, 3mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 120 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 2
In the polymerizing pipe of 10ml, add L-rac-Lactide (0.720g, 5mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 120 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through hydrogen spectrum qualification (accompanying drawing 3).
Embodiment 3
In the polymerizing pipe of 10ml, add L-rac-Lactide (2.880g, 20mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 120 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 4
In the polymerizing pipe of 10ml, add trimethylene carbonate (0.306g, 3mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 50 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 5
In the polymerizing pipe of 10ml, add trimethylene carbonate (0.510g, 5mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 50 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through hydrogen spectrum qualification (accompanying drawing 4).
Embodiment 6
In the polymerizing pipe of 10ml, add trimethylene carbonate (2.040g, 20mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 50 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 7
In the polymerizing pipe of 10ml, add δ-valerolactone (270 μ L, 3mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 8
In the polymerizing pipe of 10ml, add δ-valerolactone (450 μ L, 5mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 9
In the polymerizing pipe of 10ml, add δ-valerolactone (1.80mL, 20mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 10
In the polymerizing pipe of 10ml, add 6-caprolactone (318.3 μ L, 3mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 11
In the polymerizing pipe of 10ml, add 6-caprolactone (530.5 μ L, 5mmol), two fluoroform sulfimide calcium (0.053g, 1.0mmol), phenylcarbinol (10.3 μ L, 1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Embodiment 10
In the polymerizing pipe of 10ml, add 6-caprolactone (2.12mL, 20mmol), two fluoroform sulfimide calcium (0.053g, 0.1mmol), phenylcarbinol (10.3 μ L, 0.1mmol), mechanical stirring 24 hours under condition at 80 DEG C, after reaction terminates, termination reaction, the crude product of gained slowly instills cold methanol, there is polymkeric substance to separate out, obtain polymkeric substance through centrifugal drying, eventually through the qualification of hydrogen spectrum.
Claims (8)
1. a method for polyester is prepared in ring-opening polymerization, it is characterized in that: utilize cyclic ester as reaction monomers, and two fluoroform sulfimide salt, as catalyzer, utilizes organic alcohol roh as initiator, carries out bulk polymerization and obtains polyester.
2. prepare the method for polyester as claimed in claim 1, it is characterized in that, described cyclic ester comprises lactone, carbonic ether, lactide.
3. prepare the method for polyester as claimed in claim 2, it is characterized in that, described lactone is butyrolactone, valerolactone, caprolactone; Described carbonic ether is trimethylene carbonate, dimethyl carbonate, diethyl carbonate; Described lactide is glycollide, rac-Lactide.
4. prepare the method for polyester as claimed in claim 3, it is characterized in that, described lactone is δ-valerolactone, 6-caprolactone; Described carbonic ether is trimethylene carbonate; Described lactide is L-rac-Lactide.
5. prepare the method for polyester as claimed in claim 1, it is characterized in that, the R in described organic alcohol roh is alkyl or phenyl, and described alkyl is have the straight chain of 1 to 22 carbon atom, side chain or closed chain.
6. prepare the method for polyester as claimed in claim 5, it is characterized in that, described Organic Alcohol is methyl alcohol, ethanol, tetramethylolmethane, butynol, phenylpropyl alcohol, phenylcarbinol.
7. the method preparing polyester as described in claim 1 to 6 any one, it is characterized in that, described two fluoroform sulfimide salt are two fluoroform sulfimide calcium, two fluoroform sulfimide magnesium, two fluoroform sulfimide lithium, two fluoroform sulfimide aluminium, two fluoroform sulfimide zinc, two fluoroform sulfimide copper, two fluoroform sulfimide sodium, two fluoroform sulfimide potassium.
8. the method preparing polyester as described in claim 1 to 6 any one, it is characterized in that, described method temperature of reaction is 40 ~ 120 DEG C, reaction times is 1 ~ 24 hour, and the mol ratio of described monomer, two fluoroform sulfimide salt, Organic Alcohol is (30: 1: 1) ~ (200: 1: 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510922282.5A CN105384919A (en) | 2015-12-14 | 2015-12-14 | Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510922282.5A CN105384919A (en) | 2015-12-14 | 2015-12-14 | Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105384919A true CN105384919A (en) | 2016-03-09 |
Family
ID=55417731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510922282.5A Pending CN105384919A (en) | 2015-12-14 | 2015-12-14 | Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384919A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121799A (en) * | 2019-12-31 | 2021-07-16 | 中国科学院上海有机化学研究所 | Application of bis (fluorosulfonyl) imide as catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171271A (en) * | 2008-07-31 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Catalytic process for polymerising cyclic carbonates issued from renewable resources |
| CN102753600A (en) * | 2009-12-08 | 2012-10-24 | 阿克马法国公司 | Method for preparing a polymer from at least one cyclic monomer |
| CN104497280A (en) * | 2015-01-06 | 2015-04-08 | 济南大学 | Preparation method of polyglycolide |
| JP2015131967A (en) * | 2008-07-31 | 2015-07-23 | ピュラック バイオケム ビー． ブイ． | Process for continuous production of polyesters |
-
2015
- 2015-12-14 CN CN201510922282.5A patent/CN105384919A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171271A (en) * | 2008-07-31 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Catalytic process for polymerising cyclic carbonates issued from renewable resources |
| JP2015131967A (en) * | 2008-07-31 | 2015-07-23 | ピュラック バイオケム ビー． ブイ． | Process for continuous production of polyesters |
| CN102753600A (en) * | 2009-12-08 | 2012-10-24 | 阿克马法国公司 | Method for preparing a polymer from at least one cyclic monomer |
| CN104497280A (en) * | 2015-01-06 | 2015-04-08 | 济南大学 | Preparation method of polyglycolide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121799A (en) * | 2019-12-31 | 2021-07-16 | 中国科学院上海有机化学研究所 | Application of bis (fluorosulfonyl) imide as catalyst |
| CN113121799B (en) * | 2019-12-31 | 2022-07-19 | 中国科学院上海有机化学研究所 | Application of bis (fluorosulfonyl) imide as catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408685B (en) | Exfoliated polynite/maleic anhydride-styrene ionomer and its preparation method and application | |
| JP6509448B1 (en) | Modified polylactic acid, polymerized modified polylactic acid, and method and apparatus for producing the same | |
| Hu et al. | Preparation of zirconium and hafnium complexes containing chiral N atoms from asymmetric tertiary amine ligands, and their catalytic properties for polymerization of rac-lactide | |
| CN101747314B (en) | Process method for synthesizing L-lactide by molecular sieve catalytic pyrolysis method | |
| CN106188507A (en) | A kind of synthetic method of high molecular cyclic polylactic acid | |
| CN110483753B (en) | L ewis acid-base system controllable catalysis O-carboxylic anhydride monomer ring-opening polymerization method based on metal salt and organic base | |
| CN108503803B (en) | A method of poly- γ-fourth lactones is prepared using urea/alkoxide | |
| Yao et al. | Ring opening polymerization of l-lactide by an electron-rich Schiff base zinc complex: An activity and kinetic study | |
| CN105384919A (en) | Method for preparing polyester through catalyzing ring-opening polymerization by bis(trifluoromethylsulfonyl)imide | |
| CN106496538B (en) | Synthesis method of high molecular weight polycaprolactone | |
| Peng et al. | Isoselective mechanism for asymmetric kinetic resolution polymerization of rac-lactide catalyzed by chiral tridentate bis (oxazolinylphenyl) amido ligand supported zinc complexes | |
| CN102875779B (en) | Process method for synthesizing medical biodegradable polylactic acid by performing polycondensation on lactic acid through catalysis of 1,5,7-triazabicyclo[4.4.0]decane-5-ene (TBD) | |
| Sheng et al. | Synthesis and molecular structure of new heterometal alkoxide clusters Ln2Na8 (OCH2CF3) 14 (THF) 6 (Ln= Sm, Y, Yb): highly active catalysts for polymerization of ε-caprolactone and trimethylene carbonate | |
| CN104231234A (en) | Aminopyrrole zinc-lithium bimetallic catalyst, preparation method and application thereof | |
| CN113527650B (en) | Method for catalyzing glycolide-lactide copolymerization by acid-base pair catalyst | |
| CN103524724B (en) | Carbon-dioxide-based polycarbonate material with optical activity as well as preparation method and application thereof | |
| Hu et al. | Ring-opening polymerization of rac-lactide catalyzed by magnesium and zinc complexes supported by an NNO ligand | |
| CN106633019B (en) | Application of the cobalt complex in lactone, acrylate reactive polymerization and the copolymerization of two monomers | |
| CN104497280B (en) | A kind of preparation method of PGA | |
| CN102702488A (en) | Preparation method for polylactic acid | |
| CN105061501A (en) | Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization | |
| Liu et al. | The homoleptic bis (β-quinolylenolate) zinc catalysts for the ring-opening polymerization of ε-caprolactone: Kinetics and mechanism | |
| CN105399932A (en) | Method for preparing polylactone through ring-opening polymerization | |
| CN107586382B (en) | Zinc catalyst for preparing poly (trimethylene carbonate) | |
| Liu et al. | An intensification and integration process of preparing thermal stable polylactide end-capped by phosphate ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160309 |
|
| RJ01 | Rejection of invention patent application after publication |