CN107840945A - A kind of method that PLA is prepared by lactide - Google Patents
A kind of method that PLA is prepared by lactide Download PDFInfo
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- CN107840945A CN107840945A CN201610826893.4A CN201610826893A CN107840945A CN 107840945 A CN107840945 A CN 107840945A CN 201610826893 A CN201610826893 A CN 201610826893A CN 107840945 A CN107840945 A CN 107840945A
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- pla
- lactide
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- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/87—Non-metals or inter-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
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- 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)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention relates to a kind of method that PLA is prepared by lactide, its parts by weight composition is as follows：100 parts of lactide, 1 10 parts of catalyst, 1 10 parts of initiator；The present invention is to utilize bifunctional catalyst, a part of structure of catalyst is as electrophilic reagent activated monomer, and another part attracts initiator/end of the chain by hydrogen bond action, activate monomer and initiator/end of the chain simultaneously, dual activation is issued to open loop purpose, this reaction mechanism is similar with metal alkoxide catalyst catalytic phase, one metastable intermediate is obtained by synergy, reaction is promoted to be accelerated along this low energy path, excellent catalytic effect, both sides can be catalyzed simultaneously, and there is spatial selectivity, using such catalyst can direct polymerization HMW PLA.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field, is related to a kind of side that PLA is prepared by lactide
Method, and in particular to promote lactide ring-opening polymerisation to prepare PLA with difunctional activation initiation/catalyst system and catalyzing.
Background technology
PLA（PLA）It is a kind of new biodegradation material, uses reproducible plant resources（Such as corn）Carried
The starch material gone out is made.Lactic acid is made via fermentation process in starch material, then is converted into PLA by chemical synthesis.It has
There is good biodegradability, can be degradable by microorganism in nature after use, carbon dioxide and water are ultimately generated, no
Environment is polluted, this is highly beneficial to environmental protection, is generally acknowledged environment-friendly material.
PLA mechanical performance and physical property are good.PLA is applied to the various processing methods such as blowing, thermoplastic, processing
Convenient, application is quite varied.Compatibility is good with degradability.PLA is also very extensive in field of medicaments application, can such as give birth to
Production disposable infusion apparatus, exempt to tear type operation suture thread etc. open, low molecular weight pdlla makees medicament slow release packaging agent etc..PLA
（PLA）In addition to the basic characteristic for having biodegradable plastic, oneself unique characteristic is also equipped with.Traditional biological is degradable
Intensity, transparency and the resistivity to climate change of plastics are all not so good as in general plastics.PLA（PLA）Synthesized with petrochemical industry
The basic physical properties of plastics are similar, that is to say, that it can be widely used to make various application products.PLA also possesses well
Glossiness and transparency, and using polystyrene it is made film it is suitable, other biodegradable products can not provide.
PLA（PLA）With most good tensile strength and extensibility, PLA can also various common process modes produce, example
Such as：Extrusion molding, ejection formation, blowfilm shaping, foaming and vacuum forming are melted, with used polymer extensive at present
There is similar molding condition, it also has and conventional films identical printing performance in addition.PLA（PLA）Film has good
Gas permeability, oxygen permeability and the carbon of saturating dioxy two, it also have isolation smell characteristic.PLA is uniquely with excellent antibacterial
And the biodegradable plastic of anti-mildew characteristic.
The preparation method of PLA mainly includes direct polymerization method and lactide ring-opening polymerisation method.Direct polymerization method has poly-
Lactic origin is wide, cheap.Technique simply waits a little, and still, with the progress of reaction, whole reaction system viscosity rises,
So as to be difficult to eliminate the water in reaction system, and then it is difficult to the PLA for obtaining HMW.Lactide ring-opening polymerisation method can obtain
The PLA for the sub- amount that secures satisfactory grades, but it need to obtain the lactide of high-purity by consuming the complicated purification process of a large amount of solvents.Cause
This, compared to direct polymerization method, has the deficiencies of investment is big, complex process.The with high investment and technique of lactide polymerization is answered
It is miscellaneous seriously to limit application of this method in synthesizing polylactic acid field, with the high speed development of modern industry, invest small and technique
Simple direct polymerization method synthesizing polylactic acid gradually causes the attention of researcher.
It is therefore an object of the present invention to provide a kind of lactide ring-opening polymerisation PLA preparation method.This method catalyst
For double-functional group catalyst, initiator is aromatic alcohol, and reaction dissolvent is that fatty alcohol is reacted, at ambient temperature can be efficient
Water caused by elimination reaction, synthesis technique is simple, investment is low, simple to operate, has a good application prospect.
The content of the invention
There is the rising of reaction system viscosity for direct polymerization method, so as to be difficult to eliminate the water in reaction system, Jin Ernan
The problem of to obtain the PLA of HMW.The present invention proposes a kind of lactide ring-opening polymerisation PLA preparation method.Its
It is characterised by, using difunctional activation initiation/catalyst system and catalyzing catalyzing ring-opening polymerization of lactide, obtaining pure white powder
PLA.Both it had been avoided that in organo-aluminium, pink salt class, IV B races metal class or rare earth compound catalyst there is metal residual, poison
Property the problems such as, while have the advantages that again efficiently, reaction it is controllable.
The present invention it is a kind of PLA is prepared by lactide the specific preparation process of method it is as follows：
1）The preparation of bifunctional catalysis' agent
Binaphthol and PCl5 are weighed into sealing reaction tube, distilled protonic solvent is added at room temperature, waits and be completely dissolved
Heating stirring afterwards, after be cooled to room temperature, add binaphthol, be heated to react, cool down, transfer, be spin-dried for, obtain light brown and consolidate
Body powder.
2）The preparation of PLA
Aromatic alcohol is weighed, bifunctional catalysis' agent and lactide are added to protonic solvent stirring and form suspension for a moment,
72 hours at room temperature, light tan solid is obtained, tetrahydrofuran is added into the mixture of reaction, filters, washed with cold methanol solution
Product is washed, finally gives white solid powder.
Such catalyst part can attract the ε-CL of two equivalents by hydrogen bond action, and another part can be used as parent
The end of the chain of electric reagent activated initiator, promotes C-O mutually to pull final fracture, and monomolecular catalytic finishes, and other monomers are also herein
When insertion increase main chain, the catalyst of 1 equivalent can bilateral catalysis simultaneously, catalytic effect is high, and reaction effect is preferable, and by with
Upper data understand obtain molecular weight is of a relatively high, PDI values it is smaller be molecular weight distribution it is narrower.
The characteristics of present invention is prominent is：Described catalyst is double-functional group catalyst
In the present invention, described solvent is fatty alcohol, such as methanol, ethanol, ethylene glycol etc..
In the present invention, described initiator is aromatic alcohol, such as phenmethylol, benzyl carbinol and its derivative
In the present invention, described polymerization can water caused by efficient removal polycondensation reaction.
In the present invention, described polymerization advantage is to carry out at room temperature.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
1）The preparation of bifunctional catalysis' agent
Weigh the g of binaphthol 0.02844（0.1 mmol, 1eq）And the g of PCl5 0.02360（0.1 mmol, 1eq）It is anti-to sealing
Ying Guanzhong, distilled toluene is added at room temperature（1 ml）, wait be heated to after being completely dissolved 50 DEG C stir 1 hour, after be cooled to
Room temperature, add the g of binaphthol 0.04265（0.15 mmol, 1.5eq）, be heated to 110 DEG C reaction 12 hours after, cooling,
Transfer, is spin-dried for, obtains light tan solid powder.
2）The preparation of PLA
Weigh the mg of phenmethylol 12（0.11 mmol）, the mg of bifunctional catalysis' agent 116（0.186 mmol）With the mg of lactide 422
（3.7 mmol）The methanol solution stirring for being added to 2 ml forms suspension for a moment, 72 hours at room temperature, obtains light brown and consolidates
Body, tetrahydrofuran is added into the mixture of reaction, filters, with cold methanol solution cleaning product, finally gives white solid powder
End.
Product characterization result is Mn (g/mol)：9246, PDI：1.19.
Embodiment 2
1）The preparation of bifunctional catalysis' agent
Weigh the g of binaphthol 0.02844（0.1 mmol, 1eq）And the g of PCl5 0.02360（0.1 mmol, 1eq）It is anti-to sealing
Ying Guanzhong, distilled toluene is added at room temperature（1 ml）, wait be heated to after being completely dissolved 50 DEG C stir 1 hour, after be cooled to
Room temperature, add the g of binaphthol 0.04265（0.15 mmol, 1.5eq）, be heated to 110 DEG C reaction 12 hours after, cooling,
Transfer, is spin-dried for, obtains light tan solid powder.
2）The preparation of PLA
Weigh the mg of phenmethylol 12（0.11 mmol）, the mg of bifunctional catalysis' agent 58（0.093 mmol）With the mg of lactide 422
（3.7 mmol）The methanol solution stirring for being added to 2 ml forms suspension for a moment, 36 hours at room temperature, obtains light brown and consolidates
Body, tetrahydrofuran is added into the mixture of reaction, filters, with cold methanol solution cleaning product, finally gives white solid powder
End.
Product characterization result is Mn (g/mol)：9848, PDI：1.13.
Embodiment 3
1）The preparation of bifunctional catalysis' agent
Weigh the g of binaphthol 0.02844（0.1 mmol, 1eq）And the g of PCl5 0.02360（0.1 mmol, 1eq）It is anti-to sealing
Ying Guanzhong, distilled toluene is added at room temperature（1 ml）, wait be heated to after being completely dissolved 50 DEG C stir 1 hour, after be cooled to
Room temperature, add the g of binaphthol 0.04265（0.15 mmol, 1.5eq）, be heated to 110 DEG C reaction 12 hours after, cooling,
Transfer, is spin-dried for, obtains light tan solid powder.
2）The preparation of PLA
Weigh the mg of phenmethylol 12（0.11 mmol）, the mg of bifunctional catalysis' agent 58（0.093 mmol）With the mg of lactide 422
（3.7 mmol）The methanol solution stirring for being added to 2 ml forms suspension for a moment, 72 hours at 90 DEG C, obtains light brown and consolidates
Body, tetrahydrofuran is added into the mixture of reaction, filters, with cold methanol solution cleaning product, finally gives white solid powder
End.
Product characterization result is Mn (g/mol)：1796, PDI：1.15.
Claims (5)
- A kind of 1. method that PLA is prepared by lactide, it is characterised in that using difunctional activation initiation/catalyst system and catalyzing catalysis Lactide ring-opening polymerisation, obtain the PLA of pure white powder.
- 2. according to a kind of method that PLA is prepared by lactide described in claim 1, it is characterised in that described preparation Method comprises the following steps：1）The preparation of bifunctional catalysis' agentBinaphthol and PCl5 are weighed into sealing reaction tube, distilled protonic solvent is added at room temperature, waits and be completely dissolved Heating stirring afterwards, after be cooled to room temperature, add binaphthol, be heated to react, cool down, transfer, be spin-dried for, obtain light brown and consolidate Body powder；2）The preparation of PLAAromatic alcohol is weighed, bifunctional catalysis' agent and lactide are added to protonic solvent stirring and form suspension for a moment, 72 hours at room temperature, light tan solid is obtained, tetrahydrofuran is added into the mixture of reaction, filters, washed with cold methanol solution Product is washed, finally gives white solid powder.
- 3. according to a kind of method that PLA is prepared by lactide described in claim 1 or 2, it is characterised in that described urges Agent is double-functional group catalyst.
- 4. according to a kind of method that PLA is prepared by lactide described in claim 1 or 2, it is characterised in that described is molten Agent is fatty alcohol.
- 5. according to a kind of method that PLA is prepared by lactide described in claim 1 or 2, it is characterised in that described draws Hair agent is aromatic alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610826893.4A CN107840945A (en) | 2016-09-18 | 2016-09-18 | A kind of method that PLA is prepared by lactide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610826893.4A CN107840945A (en) | 2016-09-18 | 2016-09-18 | A kind of method that PLA is prepared by lactide |
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| Publication Number | Publication Date |
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| CN107840945A true CN107840945A (en) | 2018-03-27 |
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| CN201610826893.4A Pending CN107840945A (en) | 2016-09-18 | 2016-09-18 | A kind of method that PLA is prepared by lactide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117164550A (en) * | 2023-11-02 | 2023-12-05 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478928A (en) * | 2015-08-26 | 2017-03-08 | 黑龙江鑫达企业集团有限公司 | Polylactic acid passes through the preparation method of lactide ring-opening polymerisation method |
-
2016
- 2016-09-18 CN CN201610826893.4A patent/CN107840945A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478928A (en) * | 2015-08-26 | 2017-03-08 | 黑龙江鑫达企业集团有限公司 | Polylactic acid passes through the preparation method of lactide ring-opening polymerisation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117164550A (en) * | 2023-11-02 | 2023-12-05 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
| CN117164550B (en) * | 2023-11-02 | 2024-01-26 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
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