CN106478928A - Polylactic acid passes through the preparation method of lactide ring-opening polymerisation method - Google Patents
Polylactic acid passes through the preparation method of lactide ring-opening polymerisation method Download PDFInfo
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- CN106478928A CN106478928A CN201510529229.9A CN201510529229A CN106478928A CN 106478928 A CN106478928 A CN 106478928A CN 201510529229 A CN201510529229 A CN 201510529229A CN 106478928 A CN106478928 A CN 106478928A
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Abstract
The present invention relates to polylactic acid passes through the preparation method of lactide ring-opening polymerisation method, its weight portion composition is as follows：100 parts of lactide, catalyst 1-10 part, initiator 1-10 part；The present invention is to utilize bifunctional catalyst, the 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, activation monomer and initiator/end of the chain simultaneously, dual activation is issued to open loop purpose, this reaction mechanism and metal alkoxide catalyst are catalyzed similar, one metastable intermediate is obtained by synergism, promote reaction along this mental retardation path acceleration, excellent catalytic effect, both sides all can be catalyzed simultaneously, and there is spatial selectivity, using such catalyst can direct polymerization high molecular polylactic acid.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field, it is related to a kind of lactide ring-opening polymerisation polylactic acid preparation method and in particular to promoting lactide ring-opening polymerisation to prepare polylactic acid with difunctional activation initiation/catalyst system and catalyzing.
Background technology
Polylactic acid（PLA）It is a kind of new biodegradation material, because the good performance having is so that it is extensively employed in every profession and trade.Polylactic acid uses reproducible plant resourceses（As Semen Maydiss）The starch material being proposed is made.Starch material makes lactic acid via sweat, then is converted into polylactic acid by chemosynthesis.It has good biodegradability, can be degradable by microorganism in nature after use, ultimately generates carbon dioxide and water, free from environmental pollution, this is highly beneficial to environmental protection, the environment-friendly material being well recognized as.
Polylactic acid mechanical performance and physical property are good, the compatibility and degradability are good.Polylactic acid（PLA）In addition to the basic characteristic having biodegradable plastic, it is also equipped with the characteristic of oneself uniqueness.Polylactic acid（PLA）Similar with the basic physical properties of petrochemical industry synthetic plastic, in other words, it can be widely used to make various application products.Polylactic acid also has good glossiness and transparency, tensile strength the best and extensibility, and polylactic acid can also various common process modes produce, for example：Fusing extrusion molding, ejection formation, blowfilm shaping, foaming and vacuum forming, there is similar molding condition with extensive at present used polymer, it also has and conventional films identical printing performance in addition.Polylactic acid（PLA）Thin film has good breathability, oxygen permeability, and it also has the characteristic of isolation abnormal smells from the patient.Polylactic acid is that uniquely have excellent antibacterial and anti-mildew characteristic biodegradable plastic.Polylactic acid is due to having the excellent transparency and biodegradability, it is expected to for replacing nondegradable general-purpose plastics, in packaging fields such as container, thin film, the moulding material aspect such as the fiber art such as clothing, carpet, automobile ornament, and electronic apparatus shell is extensively applied.
The preparation method of polylactic acid mainly includes direct polymerization method and lactide ring-opening polymerisation method.Direct polymerization method shortcoming, it is obvious that with the carrying out reacting, whole reaction system viscosity rises, thus being difficult to eliminate the water in reaction system, and then is difficult to obtain the polylactic acid of high molecular.Lactide ring-opening polymerisation method can obtain the polylactic acid of high molecular, but it need to obtain highly purified lactide by consuming the complicated purification process of a large amount of solvents.Therefore, compared to direct polymerization method, there is investment greatly, the deficiency such as complex process.The with high investment and complex process of lactide polymerization seriously limits the application in synthesizing polylactic acid field for the method, with the high speed development of modern industry, invests the attention that little and process is simple direct polymerization method synthesizing polylactic acid gradually causes researcher.
Therefore, it is an object of the invention to provide a kind of lactide ring-opening polymerisation polylactic acid preparation method.The method catalyst is double-functional group catalyst, and initiator is aromatic alcohol, and reaction dissolvent reacted for fatty alcohol, at ambient temperature can water that efficiently elimination reaction produces, synthesis technique simply, invest low, simple to operate, have a good application prospect.
Content of the invention
For direct polymerization method, there is reaction system viscosity to rise, thus being difficult to eliminate the water in reaction system, and then being difficult to obtain the problem of the polylactic acid of high molecular.The present invention proposes a kind of lactide ring-opening polymerisation polylactic acid preparation method.It is characterized in that using difunctional activation initiation/catalyst system and catalyzing catalyzing ring-opening polymerization of lactide, obtaining the polylactic acid of pure white powder.Both it had been avoided that in organo-aluminium, pink salt class, IV B race metal class or rare earth compound catalyst there is the problems such as metal residual, toxicity, had the advantages that efficient, reaction was controlled simultaneously again.
A kind of concrete preparation process of present invention lactide ring-opening polymerisation polylactic acid preparation method is as follows：
1）The preparation of bifunctional catalysis' agent
Weigh binaphthol and PCl5To sealing reaction tube in, add distilled protonic solvent under room temperature, wait be completely dissolved post-heating stirring, after be cooled to room temperature, add binaphthol, be heated to reaction, cooling, transfer, be spin-dried for, obtain light tan solid powder.
2）The preparation of polylactic acid
Weigh aromatic alcohol, bifunctional catalysis' agent and lactide are added to protonic solvent stirring and form suspension for a moment, 72 hours at room temperature, obtain light tan solid, add oxolane toward in the mixture of reaction, filter, with cold methanol solution cleaning product, finally give white solid powder.
Such catalyst part can attract the lactide of two equivalents by hydrogen bond action, and another part can be used as the end of the chain of electrophilic reagent activated initiator, C-O is promoted mutually to pull final fracture, monomolecular catalytic finishes, and also insertion at this moment makes main chain increase to other monomers, and the catalyst of 1 equivalent can bilateral be catalyzed simultaneously, catalytic effect is high, reaction effect preferably, and by data above understand to obtain molecular weight is of a relatively high, PDI value is less to be that molecular weight distribution is narrower.
The feature that the present invention projects 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 benzyl alcohol, phenethanol and its derivant
In the present invention, described polymerization can the water that produces of efficient removal polycondensation reaction.
In the present invention, described polymerization advantage is to carry out at room temperature.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below.In the case of without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Embodiment 1
1）The preparation of bifunctional catalysis' agent
Weigh binaphthol 0.05684 g（0.2 mmol）And PCl50.04782 g（0.2 mmol）To in sealing reaction tube, under room temperature, add distilled toluene（2ml）, wait be completely dissolved post-heating to 50 DEG C stir 1 hour, after be cooled to room temperature, add binaphthol 0.08606 g（0.3 mmol）, after being heated to 110 DEG C of reactions 12 hours, cooling, transfer, it is spin-dried for, obtain light tan solid powder.
2）The preparation of polylactic acid
Weigh benzyl alcohol 24 mg（0.22 mmol）, bifunctional catalysis' agent 232 mg（0.373 mmol）With lactide 844 mg（7.4 mmol）The methanol solution stirring being added to 4 ml forms suspension for a moment, 72 hours at room temperature, obtains light tan solid, adds oxolane, filter, with cold methanol solution cleaning product, finally give white solid powder toward in the mixture of reaction.
Product characterization result is, Mn(g/mol) ：9301, PDI：1.20.
Embodiment 2
1）The preparation of bifunctional catalysis' agent
Weigh binaphthol 0.05684 g（0.2 mmol）And PCl50.04782 g（0.2 mmol）To in sealing reaction tube, under room temperature, add distilled toluene（2ml）, wait be completely dissolved post-heating to 50 DEG C stir 1 hour, after be cooled to room temperature, add binaphthol 0.08606 g（0.3 mmol）, after being heated to 110 DEG C of reactions 12 hours, cooling, transfer, it is spin-dried for, obtain light tan solid powder.
2）The preparation of polylactic acid
Weigh benzyl alcohol 24 mg（0.22 mmol）, bifunctional catalysis' agent 119 mg（0.184 mmol）With lactide 843 mg（7.4 mmol）The methanol solution stirring being added to 4 ml forms suspension for a moment, 36 hours at room temperature, obtains light tan solid, adds oxolane, filter, with cold methanol solution cleaning product, finally give white solid powder toward in the mixture of reaction.
Product characterization result is, Mn(g/mol) ：9835, PDI：1.16.
Embodiment 3
1）The preparation of bifunctional catalysis' agent
Weigh binaphthol 0.05684 g（0.2 mmol）And PCl50.04782 g（0.2 mmol）To in sealing reaction tube, under room temperature, add distilled toluene（2ml）, wait be completely dissolved post-heating to 50 DEG C stir 1 hour, after be cooled to room temperature, add binaphthol 0.08606 g（0.3 mmol）, after being heated to 110 DEG C of reactions 12 hours, cooling, transfer, it is spin-dried for, obtain light tan solid powder.
2）The preparation of polylactic acid
Weigh benzyl alcohol 24 mg（0.22 mmol）, bifunctional catalysis' agent 119 mg（0.184 mmol）With lactide 843 mg（7.4 mmol）The methanol solution stirring being added to 4 ml forms suspension for a moment, 72 hours at 90 DEG C, obtains light tan solid, adds oxolane, filter, with cold methanol solution cleaning product, finally give white solid powder toward in the mixture of reaction.
Product characterization result is, Mn(g/mol) ：1775, PDI：1.09.
Claims (5)
1. polylactic acid passes through the preparation method of lactide ring-opening polymerisation method it is characterised in that using difunctional activation initiation/catalyst system and catalyzing catalyzing ring-opening polymerization of lactide, obtaining the polylactic acid of pure white powder.
2. a kind of lactide ring-opening polymerisation polylactic acid preparation method according to claim 1 is it is characterised in that described preparation method comprises the steps：
1
）The preparation of bifunctional catalysis' agent
Weigh binaphthol and PCl5To sealing reaction tube in, add distilled protonic solvent under room temperature, wait be completely dissolved post-heating stirring, after be cooled to room temperature, add binaphthol, be heated to reaction, cooling, transfer, be spin-dried for, obtain light tan solid powder；
2
）The preparation of polylactic acid
Weigh aromatic alcohol, bifunctional catalysis' agent and lactide are added to protonic solvent stirring and form suspension for a moment, 72 hours at room temperature, obtain light tan solid, add oxolane toward in the mixture of reaction, filter, with cold methanol solution cleaning product, finally give white solid powder.
3. the polylactic acid according to claim 1 or 2 passes through the preparation method of lactide ring-opening polymerisation method it is characterised in that described catalyst is double-functional group catalyst.
4. the polylactic acid according to claim 1 or 2 passes through the preparation method of lactide ring-opening polymerisation method it is characterised in that described solvent is fatty alcohol.
5. the polylactic acid according to claim 1 or 2 passes through the preparation method of lactide ring-opening polymerisation method it is characterised in that described initiator is aromatic alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840945A (en) * | 2016-09-18 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | 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 |
|---|---|---|---|---|
| CN107840945A (en) * | 2016-09-18 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of method that PLA is prepared by lactide |
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Application publication date: 20170308 |
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