CN102532837B - Preparation method for high molecular weight polylactic acid steric composite - Google Patents
Preparation method for high molecular weight polylactic acid steric composite Download PDFInfo
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Abstract
The invention discloses a preparation method for a high molecular weight polylactic acid steric composite. The preparation method comprises the following steps: mixing poly-levo-lactic acid and poly-dextro-lactic acid according to the weight ratio of 80:20 to 20:80; and mixing the mixture in a torque rheometer at the temperature of between 140 and 210 DEG C and at the mixing rotating speed of 10 to 120 r/min for 1 to 60 minutes so as to prepare the high molecular weight polylactic acid steric composite. The polylactic acid is not plastified or not completely plastified at the mixed temperature; and strong interaction occurs between the molecular chains of poly-levo-lactic acid and poly-dextro-lactic acid which are not plastified or not completely plastified, so that high-content even total-content steric composite is formed in the high molecular weight polylactic acid. Compared with the conventional method, the preparation method has the advantages of simplicity, high efficiency, wide application values of products and the like.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of preparation method of high molecular weight polylactic acid steric composite.
Background technology
Since entering 21 century, plastics cause polluting and the petrochemical industry resource problem has become the focus of world wide concern, and the Biodegradable polymer material of the Sustainable development that biomass and natural resource are raw material of take becomes research and the application development direction of jointly attracting attention in the world.
Poly(lactic acid) (PLA) is the maximum kind of application in current synthesising biological degradable high polymer material, and part replaces polyolefine and is widely used in the general-purpose plastics field gradually.But some performances of poly(lactic acid) itself need to improve, and as poor as the resistance toheat of poly(lactic acid), the heat-drawn wire of the polylactic acid article obtained by injection moulding method only has 58 ℃ of left and right, and this has greatly limited the range of application of poly(lactic acid).At present main by improving poly(lactic acid) degree of crystallinity, carry out with the heat resistant type polymkeric substance thermotolerance that blend, radiation crosslinking, the method such as nano combined improve poly(lactic acid), and adopt the Stereocomplex technology, be the direction of development in recent years heat-resistance polylactic acid.
The polylactic acid stereoscopic composite that PLLA and poly-dextrolactic acid form, due to its distinctive crystalline structure, the fusing point ratio fusing point of homopolymer separately exceeds 50 ℃, has effectively improved the thermotolerance of poly(lactic acid).Simultaneously this Stereocomplex also gets a promotion the mechanical property, crystal property, hydrolytic resistance etc. of poly(lactic acid).
Yet, the formation of polylactic acid stereoscopic composite is subject to PLLA and poly-dextrolactic acid blending ratio, and (the optimum mixture ratio example such as is at the weight ratio, for the composition of PLLA/poly-dextrolactic acid system is all the precondition of stereoscopic composite), the restriction of the factors such as forming method (the most frequently used is solution casting method and melt blended method) and the molecular weight of poly(lactic acid) own.Generally, in PLLA/poly-dextrolactic acid system, both form the Stereocomplex crystal, formed again homopolymer crystal separately.When selecting optimum mixture ratio example (weight ratio 1: 1), adopt solution casting method to form to form while all being stereoscopic composite to be limited to 40000g/mol on its polylactic acid molecule amount, and be only 6000g/mol while adopting melt blended method.Research work show in a large number, and the more melt blended method of solution manufacturing method more is conducive to form stereoscopic composite.The method prepared by solution is easy and simple to handle, but aftertreatment is comparatively complicated, and cost is higher, and productive rate is lower, is not easy to large-scale commercial production.
Simultaneously, while adopting solution preparation and melt blended method, due to it, to the polylactic acid molecule quantitative limitation, stereoscopic composite prepared by low molecular weight is fragility, has limited the range of application of polylactic acid stereoscopic composite.CN101712763A discloses employing direct melt polycondensation method and has prepared PLLA and poly-dextrolactic acid prepolymer, then utilizes melt blending to generate Stereocomplex, and the recycling solid state polymerization improves the method for the molecular weight of product.
Summary of the invention
The invention provides a kind of preparation method of high molecular weight polylactic acid steric composite.Preparation method's technique simple possible provided by the invention, having overcome polylactic acid stereoscopic composite preparation method in the past, in the restriction of the aspects such as polylactic acid molecule amount, PLLA and poly-dextrolactic acid blending ratio, forming method, has preparation method's (solution manufacturing method, melt blended method) and has very big advantage.
High molecular weight polylactic acid steric composite preparation method provided by the invention comprises following technical scheme:
PLLA is mixed by weight with poly-dextrolactic acid in 80: 20～20: 80; And mixture is mixed in torque rheometer under 140～210 ℃ of conditions, the mixing rotating speed is 10～120r/min, mixing time is 1～60mim, has completed the preparation of high molecular weight polylactic acid steric composite.
Further scheme is: with before poly-dextrolactic acid mixes, PLLA and poly-dextrolactic acid are carried out to drying at PLLA, dry after the water ratio of PLLA and poly-dextrolactic acid lower than 250ppm.
Further scheme is: the described dry vacuum-drying that adopts, be that 4～48h, drying temperature are that 60～140 ℃, vacuum tightness are less than 1000Pa time of drying.
Further scheme is: the relative molecular mass of described PLLA is 10,000～500,000, optical purity is greater than 90%, and the relative molecular mass of poly-dextrolactic acid is 10,000～500,000, optical purity is greater than 90%.
In the present invention, torque rheometer is all industrial torque rheometers, it is the conventional instrument of this area, use at present commonplace torque rheometer to comprise the Haake torque rheometer of Multiple Type, the torque rheometer that Shanghai Kechuang model is XSS-300, the BRABENDER torque rheometer, torque rheometer that the model of Kazakhstan rich Electric Manufacture company is RM 200 etc.Because the principle of all torque rheometers is identical, therefore adopt which kind of torque rheometer not affect effect of the present invention.
In the present invention, mixing temperature is 140 ℃～210 ℃, and under this mixing temperature, plasticizing or not plasticizing fully do not occur poly(lactic acid).And plasticizing does not occur or do not have strong interaction between the PLLA of plasticizing and poly-dextrolactic acid molecular chain fully, thereby (molecular weight is far above 10 at poly-lactic acid in high molecular weight
5g/mol) form high-content or even whole stereoscopic composites in.
The present invention has the following advantages:
1. adopt high molecular weight polylactic acid steric composite preparation method of the present invention, can at poly-lactic acid in high molecular weight, (molecular weight be far above 10
5g/mol) form high-content in, or even whole stereoscopic composites.
2. adopting melt blended method and solution manufacturing method only can form under the polylactic acid molecule Parameter Conditions of Stereocomplex crystal and homopolymer crystal, in the poly(lactic acid) that adopts preparation method of the present invention to prepare, forming is all stereoscopic composite.
3. adopt the preparation method of high molecular weight polylactic acid steric composite of the present invention, can be to form under the condition of the weight ratio such as non-that to form be all the crystal of Stereocomplex in the blending ratio of PLLA and poly-dextrolactic acid, break through the blending ratio of PLLA and poly-dextrolactic acid while preparing polylactic acid stereoscopic composite and limited.
4. the poly-lactic acid in high molecular weight that adopts preparation method of the present invention to prepare, its overall crystallinity (approximately 50%) is significantly higher than melt blended method (22.4%) and the prepared poly(lactic acid) of solution manufacturing method (35.4%).The increase of degree of crystallinity can improve the thermotolerance of poly(lactic acid).
5. the high molecular weight polylactic acid steric composite that adopts preparation method of the present invention to prepare, its fusing point (approximately 230 ℃) is higher than the fusing point of melt blended method (218.9 ℃) and solution manufacturing method (213.9 ℃) gained stereoscopic composite, thereby makes the thermotolerance of poly(lactic acid) further improve.
6. preparation method's technique simple possible of the present invention.
7. the preparation method of high molecular weight polylactic acid steric composite of the present invention further improves the poly(lactic acid) thermotolerance, improves mechanical property, crystal property and the hydrolytic resistance of poly(lactic acid), thereby further enlarge the poly(lactic acid) range of application, provides the foundation.
8. the existing method (solution manufacturing method, melt blended method) of preparation method of the present invention has very big advantage, especially outstanding behaviours method simple, efficiency is high, product application is worth the aspects such as wide.
The accompanying drawing explanation
The DSC melting curve that Fig. 1 is the embodiment of the present invention 1 to 3 and Comparative Examples;
The DSC melting curve that Fig. 2 is the embodiment of the present invention 4 to 6 and Comparative Examples.
Embodiment
Below provide embodiment so that the present invention is specifically described.Wherein in embodiment 1～3, PLLA and poly-dextrolactic acid blending ratio such as are at the weight ratio, and in embodiment 4～6, PLLA and poly-dextrolactic acid blending ratio are the weight ratio such as non-.The PLLA of all embodiment and Comparative Examples and poly-dextrolactic acid have all under equal conditions carried out vacuum-drying, and the water ratio of dry rear PLLA and poly-dextrolactic acid is lower than 250ppm.And the relative molecular mass of PLLA is 10,000～500,000, optical purity is greater than 90%, the relative molecular mass of poly-dextrolactic acid is 10,000～500,000, optical purity is greater than 90%.
Embodiment 1
The PLLA that weight ratio is 50: 50 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 140 ℃, and rotating speed is 40r/min, and the blend time is 15min.In preparation process, resin plastifies, and the gained sample adopts differential scanning calorimeter (DSC) to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 1.
Embodiment 2
The PLLA that weight ratio is 50: 50 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 180 ℃, and rotating speed is 40r/min, and the blend time is 15min.In preparation process, resin plastifies, and the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 1.
Embodiment 3
The PLLA that weight ratio is 50: 50 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 210 ℃, and rotating speed is 40r/min, and the blend time is 15min.Plasticizing fully of resin in preparation process, the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 1.
Embodiment 4
The PLLA that weight ratio is 60: 40 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 160 ℃, and rotating speed is 40r/min, and the blend time is 15min.Plasticizing fully of resin in preparation process, the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 2.
Embodiment 5
The PLLA that weight ratio is 70: 30 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 160 ℃, and rotating speed is 40r/min, and the blend time is 15min.Plasticizing fully of resin in preparation process, the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 2.
Embodiment 6
The PLLA that weight ratio is 80: 20 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 160 ℃, and rotating speed is 40r/min, and the blend time is 15min.Plasticizing fully of resin in preparation process, the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 2.
Comparative Examples 1
The PLLA that weight ratio is 50: 50 and poly-dextrolactic acid resin carry out blend in torque rheometer, and blending temperature is 220 ℃, and rotating speed is 40r/min, and the blend time is 15min.In preparation process, resin plastifies fully, and the gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 1, Fig. 2.
Comparative Examples 2
The PLLA that weight ratio is 50: 50 and poly-dextrolactic acid resin are dissolved in respectively in dichloromethane solvent, are poured into film after solution blending.The gained sample adopts DSC to be heated to 250 ℃ of meltings with 10 ℃/min, and it the results are shown in Table 1 and Fig. 1, Fig. 2.
In table 1. embodiment 1～6 and Comparative Examples 1～2 by the parameter of DSC melting curve gained
Annotate: T
ccfor cold crystallization peak temperature, Δ H
ccfor cold crystallization heat content, T
mfor the melting peak temperature, Δ H
mfor melting enthalpy, X
cfor overall crystallinity, 1 represents the homopolymer crystal, and 2 represent Stereocomplex crystal (being stereoscopic composite).
From Fig. 1 and table 1, in the blending ratio of PLLA and poly-dextrolactic acid, be etc. under the condition of weight ratio, it in the poly-lactic acid in high molecular weight that adopts preparation method of the present invention to prepare, is all stereoscopic composite (embodiment 1～3), and both contained the Stereocomplex crystal in poly(lactic acid) while adopting melt blended method and solution manufacturing method, contain again homopolymer crystal (Comparative Examples 1,2) separately.And the overall crystallinity of the poly-lactic acid in high molecular weight that adopts preparation method of the present invention to prepare (approximately 50%) is significantly higher than melt blended method (22.4%) and the prepared poly(lactic acid) of solution manufacturing method (35.4%), and its fusing point (approximately 230 ℃) is higher than melt blended method (218.9 ℃) and solution manufacturing method (213.9 ℃) gained stereoscopic composite fusing point.
From Fig. 2 and table 1, under the condition that is the weight ratio such as non-in the blending ratio of PLLA and poly-dextrolactic acid, the content of stereoscopic composite very high (embodiment 4～6) in the poly-lactic acid in high molecular weight that adopts preparation method of the present invention to prepare, even under the condition that is 80: 20 in the weight ratio of PLLA and poly-dextrolactic acid (embodiment 6), the melting enthalpy of its Stereocomplex crystal still higher than etc. the PLLA of weight ratio and the melting enthalpy that poly-dextrolactic acid adopts the resulting Stereocomplex crystal of melt blended method (Comparative Examples 1), and with etc. the PLLA of weight ratio and poly-dextrolactic acid adopt the melting enthalpy of the resulting Stereocomplex crystal of solution manufacturing method (Comparative Examples 2) suitable.Particularly the weight ratio of PLLA and poly-dextrolactic acid is (embodiment 4) under 60: 40 conditions, and in the poly-lactic acid in high molecular weight that adopts preparation method of the present invention to prepare, crystal composition is all still stereoscopic composite.
Claims (3)
1. the preparation method of a high molecular weight polylactic acid steric composite is characterized in that:
PLLA is mixed by weight 80:20 ~ 20:80 with poly-dextrolactic acid; And mixture is mixed in torque rheometer under 140 ~ 210 ℃ of conditions, under this mixing temperature, plasticizing or not plasticizing fully do not occur in poly(lactic acid), and the mixing rotating speed is 10 ~ 120r/min, mixing time is 1 ~ 60mim, has completed the preparation of high molecular weight polylactic acid steric composite;
The relative molecular mass of described PLLA is 10,000 ~ 500,000, optical purity is greater than 90%, and the relative molecular mass of poly-dextrolactic acid is 10,000 ~ 500,000, optical purity is greater than 90%.
2. method according to claim 1 is characterized in that: with before poly-dextrolactic acid mixes, PLLA and poly-dextrolactic acid are carried out to drying at PLLA, dry after the water ratio of PLLA and poly-dextrolactic acid lower than 250ppm.
3. method according to claim 2 is characterized in that: the described dry vacuum-drying that adopts, be that 4 ~ 48h, drying temperature are that 60 ~ 140 ℃, vacuum tightness are less than 1000Pa time of drying.
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| CN104059343B (en) | 2013-03-20 | 2016-08-31 | 中国科学院化学研究所 | A kind of polylactic acid composition and moulded products thereof, preparation method, and application thereof |
| CN103333472B (en) * | 2013-07-24 | 2015-08-05 | 四川大学 | There is the preparation method of the high molecular weight polylactic acid steric composite of melt stability |
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| CN105463624B (en) * | 2015-12-28 | 2017-11-17 | 上海新宁生物材料有限公司 | The preparation method of the vertical structure rate polylactic acid stereoscopic composite of height |
| CN106280335B (en) * | 2016-08-25 | 2018-06-29 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material and its dyeing of a kind of easy coloring |
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| CN109337308B (en) * | 2018-08-30 | 2020-08-28 | 北京服装学院 | High-stereospecificity composite polylactic acid material and preparation method thereof |
| CN111534064B (en) * | 2020-04-28 | 2022-11-01 | 金旸（厦门）新材料科技有限公司 | Polylactic acid with high stereospecific composite content and preparation method thereof |
| CN111440426B (en) * | 2020-05-12 | 2023-05-05 | 中国科学院长春应用化学研究所 | Unidirectional stretching polylactic acid stereocomplex and preparation method thereof |
| CN112920575B (en) * | 2021-01-30 | 2021-12-10 | 四川大学 | All-stereo composite polylactic acid material with excellent melt stability and preparation thereof |
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