CN104045820A - Preparation method of poly(propylene carbonate) polylactic acid composite - Google Patents
Preparation method of poly(propylene carbonate) polylactic acid composite Download PDFInfo
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Abstract
The invention provides a preparation method of a poly(propylene carbonate) polylactic acid composite. The preparation method comprises the following steps: (A) carrying out reaction on poly(propylene carbonate) and an anhydride compound to obtain end-capped poly(propylene carbonate); and (B) in the presence of a catalyst, carrying out transesterification on polylactic acid and the end-capped poly(propylene carbonate) obtained in the step (A) to obtain the poly(propylene carbonate) polylactic acid composite, wherein the catalyst is a titanium-containing catalyst, a zirconium-containing catalyst, an antimony-containing catalyst or an organic tin catalyst. According to the preparation method provided by the invention, the poly(propylene carbonate) is end-capped, and when the polylactic acid and the end-capped poly(propylene carbonate) are blended together, a little amount of special catalyst is added, so that the transesterification degree between the polylactic acid and the end-capped poly(propylene carbonate) can be improved, and thus the compatibility is improved and the environmental protection property is also ensured. The preparation of the high-toughness degradable poly(propylene carbonate) polylactic acid composite is realized.
Description
Technical field
The present invention relates to polypropylene carbonate technical field, particularly a kind of preparation method of polypropylene carbonate lactic acid composite material.
Background technology
Polypropylene carbonate (being called for short PPC) is the alternating copolymer of carbon dioxide-epoxy propane, belongs to biodegradable environment-friendly material.Because polypropylene carbonate has stabilizing carbon dioxide and biodegradable characteristic, it has a wide range of applications in fields such as wrapping material, fiber and health cares.At present, the copolymerization product of carbonic acid gas and propylene oxide---polypropylene carbonate has entered into the suitability for industrialized production stage.But, because the second-order transition temperature (Tg) of itself is conventionally at 30 ℃～40 ℃, and be unformed shape, there is the defects such as the large and high temperature dimensional stability of low temperature brittleness is poor, cause the mechanical properties such as the intensity of this material and toughness poor, easily degraded in the course of processing, is difficult to as plastics, use separately, thereby has limited the application of polypropylene carbonate in fields such as packing, food and medical treatment.
In order to improve the mechanical property of PPC and thermostability etc., prior art generally adopts the method for polycomponent blending and modifying.Wherein, the performance that adopts poly(lactic acid) and polypropylene carbonate blend to improve PPC is a kind of effective means, poly(lactic acid) is a kind of novel biodegradable plastic, there is the advantages such as good biocompatibility, good, the renewable and mechanical property of the transparency be balanced, can improve the mechanical property of PPC, and improve its thermostability.Such as, publication number is the preparation method that the Chinese patent literature of CN1749318A discloses a kind of poly lactic acid type composite material of ternary built completely biological degradation, the method comprises: weigh be weight % each starting material component: (A) poly(lactic acid) (PLA): 45.0～80.0, (B) polypropylene carbonate (PPC): 4.0～40.0, (C) poly 3-hydroxy butyrate (PHB): 4.0～40.0, all the other are various auxiliary agents; By matrix resin, powder material, properties-correcting agent in the starting material component weighing, in advance in baking oven 45～65 ℃ dry 6～10 hours, then by stirring at low speed 5～10 minutes in high-speed mixer, recurrence high-speed stirring is after 3～5 minutes, pack in parallel dual-screw extruding machine, in temperature, be 65～195 ℃ and carry out extruding pelletization, can obtain product.
Poly(lactic acid) and polypropylene carbonate are that thermodynamics is inconsistent, and the toughness of the blend of the two is very poor.For this reason, aforesaid method has been introduced the third high molecular component PHB, but toughening effect is limited, and has increased cost, also affects the degradation property of matrix material.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of preparation method of polypropylene carbonate lactic acid composite material, preparation method provided by the invention prepares high tenacity and degradable polypropylene carbonate lactic acid composite material, can reach toughness reinforcing and object environmental protection.
The preparation method who the invention provides a kind of polypropylene carbonate lactic acid composite material, comprises the following steps:
A) polypropylene carbonate and anhydrides compound are reacted, obtain the polypropylene carbonate of end-blocking;
B) under the existence of catalyzer, by poly(lactic acid) and described steps A) polypropylene carbonate of the end-blocking that obtains carries out transesterification reaction, obtains polypropylene carbonate lactic acid composite material; Described catalyzer is titanium-containing catalyst, zirconium-containing catalyst, antimony-containing catalyst or organic tin catalyzer.
Preferably, described steps A) in, described anhydrides compound is one or more in maleic anhydride, Succinic anhydried and Pyroglutaric acid.
Preferably, described steps A) in, the mass ratio of described polypropylene carbonate and anhydrides compound is 99/1～95/5.
Preferably, described steps A) in, the temperature of described reaction is 120 ℃～150 ℃.
Preferably, described step B) in, described titanium-containing catalyst is tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid four n-propyls, titanium isopropylate, metatitanic acid tetramethyl ester or titanium dioxide.
Preferably, described step B) in, described organic tin catalyzer is Dibutyltin oxide, dibutyl tin laurate, di-n-butylacetic acid tin or stannous octoate.
Preferably, described step B) in, the quality of described catalyzer be poly(lactic acid) and end-blocking polypropylene carbonate total mass 0.1%～5%.
Preferably, described step B) in, the mass ratio of the polypropylene carbonate of described poly(lactic acid) and end-blocking is 30/70～50/50.
Preferably, described step B) in, the temperature of described transesterification reaction is 175 ℃～200 ℃.
Preferably, described step B) in, the time of described transesterification reaction is 3min～10min.
Compared with prior art, first the present invention adopts anhydrides compound, reacts with polypropylene carbonate, completes termination process, obtains the polypropylene carbonate of end-blocking; Then itself and poly(lactic acid) are carried out to transesterification reaction under the effect of catalyzer, obtain polypropylene carbonate lactic acid composite material; Described catalyzer is titanium-containing catalyst, zirconium-containing catalyst, antimony-containing catalyst or organic tin catalyzer.The present invention carries out end-blocking to polypropylene carbonate, and, when by the polypropylene carbonate blend of poly(lactic acid) and end-blocking, add a small amount of specific catalyzer, can improve the two transesterification reaction carry out degree, thereby raising consistency, the feature of environmental protection is also guaranteed, has realized the preparation of high tenacity and degradable polypropylene carbonate lactic acid composite material.Experiment shows, the elongation at break of the matrix material that the present invention makes can be up to 180% left and right.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method who the invention provides a kind of polypropylene carbonate lactic acid composite material, comprises the following steps:
A) polypropylene carbonate and anhydrides compound are reacted, obtain the polypropylene carbonate of end-blocking;
B) under the existence of catalyzer, by poly(lactic acid) and described steps A) polypropylene carbonate of the end-blocking that obtains carries out transesterification reaction, obtains polypropylene carbonate lactic acid composite material; Described catalyzer is titanium-containing catalyst, zirconium-containing catalyst, antimony-containing catalyst or organic tin catalyzer.
The present invention is to provide the preparation method of a kind of high tenacity and degradable polypropylene carbonate lactic acid composite material, cost is lower, more environmental protection.
First the embodiment of the present invention carries out the termination process of polypropylene carbonate, namely polypropylene carbonate and anhydrides compound is put into Banbury mixer by a certain percentage, and melt blending obtains the polypropylene carbonate of end-blocking after reaction.
Polypropylene carbonate, referred to as PPC, also can be described as poly-propylene carbonate, is the alternating copolymer of carbon dioxide-epoxy propane, belongs to biodegradable environment-friendly material.For the aspects such as the polymerization degree of described polypropylene carbonate, the present invention is not particularly limited, if its polymerization degree can be 80000～10000.
The present invention adopts anhydrides compound, usings it as polypropylene carbonate end-capping reagent, and described polypropylene carbonate is carried out to end-blocking.Described anhydrides compound is preferably one or more in maleic anhydride, Succinic anhydried and Pyroglutaric acid, more preferably maleic anhydride.In the present invention, the mass ratio of described polypropylene carbonate and anhydrides compound is preferably 99/1～95/5, and more preferably 99/1.
The present invention can adopt various suitable melt-processed technique, as adopted twin screw extruder blend, or adopts Banbury mixer blend, makes polypropylene carbonate and the reaction of anhydrides compound, completes termination process.Wherein, the temperature of described reaction is preferably 120 ℃～150 ℃, more preferably 130 ℃.The time of described reaction is preferably 5min～10min, more preferably 7min.When described reaction is carried out in Banbury mixer, rotating speed is preferably 50rpm～100rpm, more preferably 80rpm.In the present invention, described termination process also can make the thermostability of PPC be improved.
Obtain after the polypropylene carbonate of end-blocking, the embodiment of the present invention is carried out the preparation of high-toughness polylactic acid/polypropylene carbonate mixture, namely the polypropylene carbonate of poly(lactic acid), end-blocking and catalyzer are put into Banbury mixer by a certain percentage, melt blending, obtains polypropylene carbonate lactic acid composite material after transesterification reaction.
Poly(lactic acid) good biocompatibility and mechanical property are balanced, by itself and polypropylene carbonate blend, can improve the mechanical property of PPC and thermal stability etc.For aspects such as the polymerization degree of described poly(lactic acid) and opticities, the present invention is not particularly limited, if its polymerization degree can be 70000～100000.In the present invention, the mass ratio of the polypropylene carbonate of described poly(lactic acid) and end-blocking is preferably 30/70～50/50, and more preferably 40/60.
The present invention is when by the polypropylene carbonate blend of poly(lactic acid) and end-blocking, add a small amount of specific catalyzer, can improve the two transesterification reaction carry out degree, thereby raising consistency, the feature of environmental protection is also guaranteed, has reached the object of preparation high tenacity and environmental protection, degradable polypropylene carbonate lactic acid composite material.
In the present invention, described catalyzer is titanium-containing catalyst, zirconium-containing catalyst, antimony-containing catalyst or organic tin catalyzer, is preferably titanium-containing catalyst, more preferably tetra-n-butyl titanate.Concrete, the positive butyl ester of catalyzer metatitanic acid four also available other compounds substitutes, be that described titanium-containing catalyst is preferably tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid four n-propyls, titanium isopropylate, metatitanic acid tetramethyl ester or titanium dioxide, more preferably tetra-n-butyl titanate.Wherein, tetra-n-butyl titanate can be described as again butyl (tetra) titanate or tetrabutyl titanate.Metatitanic acid four n-propyls can be described as again metatitanic acid orthocarbonate, and tetrabutyl titanate can be described as again iso-butyl titanate.
In catalyzer of the present invention, described organic tin catalyzer is preferably Dibutyltin oxide, dibutyl tin laurate, di-n-butylacetic acid tin or stannous octoate.Described zirconium-containing catalyst is preferably zirconium white or tetrabutyl zirconate; Described antimony-containing catalyst is as antimonous oxide etc.
The addition of described catalyzer is also more crucial, its quality optimization be described poly(lactic acid) and end-blocking polypropylene carbonate total mass 0.1%～5%, more preferably 1%～2%.In an embodiment of the present invention, the polypropylene carbonate of poly(lactic acid), end-blocking and the mass ratio of catalyzer can be 30/70/1,40/60/1,50/50/2.
The present invention can adopt various suitable melt-processed technique, as adopted twin screw extruder blend, or adopts Banbury mixer blend, makes the polypropylene carbonate of poly(lactic acid) and end-blocking, under the effect of catalyzer, transesterification reaction occur, and reaches toughening effect.Wherein, the temperature of described transesterification reaction is preferably 175 ℃～200 ℃, more preferably 180 ℃.The time of described transesterification reaction is preferably 3min～10min, more preferably 5min.When described transesterification reaction is carried out in Banbury mixer, rotating speed is preferably 50rpm～100rpm, more preferably 50rpm.
In one embodiment of the invention, by a certain percentage, by the polypropylene carbonate of poly(lactic acid), end-blocking and butyl (tetra) titanate (Ti (OBu)
4) put into Banbury mixer melt blending, after reaction under certain condition, obtain PLA-co-PPC matrix material.Reaction mechanism is suc as formula shown in (1):
In formula (1), 735≤m≤860; 1019≤n≤1108.
By the contrast of number-average molecular weight, after showing that catalyst Ti acid butyl ester adds, there is transesterification reaction in the polypropylene carbonate of poly(lactic acid) and end-blocking, and molecule chain break, rearrangement cause molecular weight to change.
Obtain after polypropylene carbonate lactic acid composite material, the present invention adopts Instron-5869 shaped material trier, at probe temperature, is under 20 ℃, the rate of extension condition that is 30mm/min, tests its elongation at break.Result demonstration, the elongation at break of the matrix material that the present invention makes can show that its tensile toughness is good up to 180% left and right, has broader range of application.
And the inventive method is easy, cost is lower, has more the feature of environmental protection.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of polypropylene carbonate lactic acid composite material provided by the invention is described in detail.
In following examples, the number-average molecular weight of polypropylene carbonate is 81016, and the number-average molecular weight of poly(lactic acid) is 73396.
Embodiment 1
Mass ratio by 99/1, the melt blending in Banbury mixer by polypropylene carbonate and maleic anhydride, the temperature of blend is 130 ℃, and the time of blend is 7min, and rotating speed is 80rpm, obtains the polypropylene carbonate of end-blocking.
Utilize thermogravimetric analyzer (TGA), the present invention tests the initial thermal degradation temperature of the polypropylene carbonate before and after end-blocking, and test condition is: under nitrogen protection, temperature rise rate is 10 ℃/minute, and Range of measuring temp is 25 ℃～500 ℃.Result demonstration, before end-blocking, the initial thermal degradation temperature of polypropylene carbonate is 150 ℃, after end-blocking, initial thermal degradation temperature is brought up to 240 ℃.
Mass ratio by 30/70/1, the polypropylene carbonate of poly(lactic acid), described end-blocking and butyl (tetra) titanate are put into Banbury mixer melt blending, the temperature of blend is 180 ℃, the time of blend is 5min, rotating speed is 50rpm, obtain polypropylene carbonate lactic acid composite material, its number-average molecular weight is 46998.
According to method mentioned above, the present invention tests the elongation at break of described matrix material.Result demonstration, the elongation at break of described matrix material is 124.8 ± 18.1%.
Comparative example 1
Mass ratio by 99/1, the melt blending in Banbury mixer by polypropylene carbonate and maleic anhydride, the temperature of blend is 130 ℃, and the time of blend is 7min, and rotating speed is 80rpm, obtains the polypropylene carbonate of end-blocking.
Mass ratio by 30/70, puts into Banbury mixer melt blending by the polypropylene carbonate of poly(lactic acid) and described end-blocking, and the temperature of blend is 180 ℃, the time of blend is 5min, rotating speed is 50rpm, obtains polypropylene carbonate lactic acid composite material, and its number-average molecular weight is 73896.
According to method mentioned above, the present invention tests the elongation at break of described matrix material.Result demonstration, the elongation at break of described matrix material is 5.2 ± 1.2%.
From above embodiment and comparative example, add after butyl (tetra) titanate catalyzer, the number-average molecular weight of blend obviously declines, and shows that transesterification reaction has occurred the polypropylene carbonate of poly(lactic acid) and end-blocking, and due to molecule chain break, rearrangement, molecular weight reduces.
And, adding after a small amount of catalyzer, prepared material has good tensile toughness, and range of application is broader.
Embodiment 2
Mass ratio by 99/1, the melt blending in Banbury mixer by polypropylene carbonate and maleic anhydride, the temperature of blend is 130 ℃, and the time of blend is 7min, and rotating speed is 80rpm, obtains the polypropylene carbonate of end-blocking.
Mass ratio by 40/60/1, the polypropylene carbonate of poly(lactic acid), described end-blocking and butyl (tetra) titanate are put into Banbury mixer melt blending, and the temperature of blend is 180 ℃, and the time of blend is 5min, rotating speed is 50rpm, obtains polypropylene carbonate lactic acid composite material.
According to method mentioned above, the present invention tests the elongation at break of described matrix material.Result demonstration, the elongation at break of described matrix material is 177.9 ± 15.3%.
Comparative example 2
Mass ratio by 99/1, the melt blending in Banbury mixer by polypropylene carbonate and maleic anhydride, the temperature of blend is 130 ℃, and the time of blend is 7min, and rotating speed is 80rpm, obtains the polypropylene carbonate of end-blocking.
Mass ratio by 40/60, puts into Banbury mixer melt blending by the polypropylene carbonate of poly(lactic acid) and described end-blocking, and the temperature of blend is 180 ℃, and the time of blend is 5min, and rotating speed is 50rpm, obtains polypropylene carbonate lactic acid composite material.
According to method mentioned above, the present invention tests the elongation at break of described matrix material.Result demonstration, the elongation at break of described matrix material is 4.4 ± 1.1%.
Embodiment 3
Mass ratio by 99/1, the melt blending in Banbury mixer by polypropylene carbonate and maleic anhydride, the temperature of blend is 130 ℃, and the time of blend is 7min, and rotating speed is 80rpm, obtains the polypropylene carbonate of end-blocking.
Mass ratio by 50/50/2, the polypropylene carbonate of poly(lactic acid), described end-blocking and butyl (tetra) titanate are put into Banbury mixer melt blending, and the temperature of blend is 180 ℃, and the time of blend is 5min, rotating speed is 50rpm, obtains polypropylene carbonate lactic acid composite material.
According to method mentioned above, the present invention tests the elongation at break of described matrix material.Result demonstration, the elongation at break of described matrix material is 108.2 ± 16.8%.
As seen from the above embodiment, the present invention carries out termination process by polypropylene carbonate, and when with poly(lactic acid) melt blending, adds a small amount of specific catalyzer, can prepare polypropylene carbonate lactic acid composite material.And the matrix material that the present invention makes has good toughness and thermostability, degradable and environmental protection, cost is lower.
In addition, preparation method provided by the invention is simple and easy to do, workable, is suitable for promoting.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a preparation method for polypropylene carbonate lactic acid composite material, comprises the following steps:
A) polypropylene carbonate and anhydrides compound are reacted, obtain the polypropylene carbonate of end-blocking;
B) under the existence of catalyzer, by poly(lactic acid) and described steps A) polypropylene carbonate of the end-blocking that obtains carries out transesterification reaction, obtains polypropylene carbonate lactic acid composite material; Described catalyzer is titanium-containing catalyst, zirconium-containing catalyst, antimony-containing catalyst or organic tin catalyzer.
2. preparation method according to claim 1, is characterized in that, described steps A) in, described anhydrides compound is one or more in maleic anhydride, Succinic anhydried and Pyroglutaric acid.
3. preparation method according to claim 1, is characterized in that, described steps A) in, the mass ratio of described polypropylene carbonate and anhydrides compound is 99/1～95/5.
4. preparation method according to claim 1, is characterized in that, described steps A) in, the temperature of described reaction is 120 ℃～150 ℃.
5. preparation method according to claim 1, is characterized in that, described step B) in, described titanium-containing catalyst is tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid four n-propyls, titanium isopropylate, metatitanic acid tetramethyl ester or titanium dioxide.
6. preparation method according to claim 1, is characterized in that, described step B) in, described organic tin catalyzer is Dibutyltin oxide, dibutyl tin laurate, di-n-butylacetic acid tin or stannous octoate.
7. preparation method according to claim 1, is characterized in that, described step B) in, the quality of described catalyzer be poly(lactic acid) and end-blocking polypropylene carbonate total mass 0.1%～5%.
8. preparation method according to claim 1, is characterized in that, described step B) in, the mass ratio of the polypropylene carbonate of described poly(lactic acid) and end-blocking is 30/70～50/50.
9. preparation method according to claim 1, is characterized in that, described step B) in, the temperature of described transesterification reaction is 175 ℃～200 ℃.
10. preparation method according to claim 1, is characterized in that, described step B) in, the time of described transesterification reaction is 3min～10min.
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| CN108424626A (en) * | 2018-01-17 | 2018-08-21 | 北京工商大学 | A kind of polylactic acid poly propylene carbonate composite material and preparation method |
| CN112063137A (en) * | 2020-08-14 | 2020-12-11 | 沈阳化工大学 | Biodegradable blending material for improving crystallinity of polylactic acid and preparation method thereof |
| CN114702638A (en) * | 2022-03-02 | 2022-07-05 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108424626A (en) * | 2018-01-17 | 2018-08-21 | 北京工商大学 | A kind of polylactic acid poly propylene carbonate composite material and preparation method |
| CN108424626B (en) * | 2018-01-17 | 2021-02-12 | 北京工商大学 | Polylactic acid and polypropylene carbonate composite material and preparation method thereof |
| CN112063137A (en) * | 2020-08-14 | 2020-12-11 | 沈阳化工大学 | Biodegradable blending material for improving crystallinity of polylactic acid and preparation method thereof |
| CN114702638A (en) * | 2022-03-02 | 2022-07-05 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
| CN114702638B (en) * | 2022-03-02 | 2024-02-13 | 中国科学院长春应用化学研究所 | Polypropylene carbonate chain-extended copolymer and preparation method thereof |
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