CN104650548A - Preparation method of high molecular weight polylactic acid material with easiness in stereocomplex crystallization - Google Patents
Preparation method of high molecular weight polylactic acid material with easiness in stereocomplex crystallization Download PDFInfo
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Abstract
The invention relates to a degradable high molecular material modification technology, and aims at providing a preparation method of a high molecular weight polylactic acid (PLA) material with easiness in stereocomplex crystallization. The method is characterized in that two components, namely multi-branched poly-D-lactic acid and linear poly-L-lactic acid or multi-branched poly-L-lactic acid, are subjected to solution blending or fusion blending to form the high molecular weight polylactic acid material, and the optical purities of the two components are greater than 95%. The fusion point of the high molecular weight polylactic acid stereocomplex material prepared by the preparation method is higher than 210 DEG C, so that the heat resistance of common polylactic acid is improved effectively, and the solvent resistance and the degradation resistance of polylactic acid can be improved. The raw materials are from biomass renewable resources, so that the high molecular weight polylactic acid material can be degraded completely after use, is green and environment-friendly, and has good biocompatibility. The high molecular weight polylactic acid material is prepared by a blending method, so that the process procedure is simple, the cost is low, and large-scale industrial production is facilitated.
Description
Technical field
The invention relates to bio-based, Biodegradable polymer material technical field of modification, particularly easy Stereocomplex crystallization, the preparation method of high heat-resisting poly-lactic acid in high molecular weight material.
Background technology
Poly(lactic acid) (PLA) has excellent biodegradability, biocompatibility, mechanical mechanics property, workability etc., is that the one of alternative conventional petroleum base polymeric material is well selected.Because the monomer of PLA has enantiomerically, therefore PLA has two kinds of enantiomer-specific structures, i.e. PLLA (PLLA) and poly-dextrolactic acid (PDLA), and wherein PLLA is more common.The fusing point of PLLA is about 170 DEG C, but due to its crystallization rate comparatively slow, in the normal melt course of processing, crystallization or degree of crystallinity are extremely low hardly for PLLA, and therefore its heat-drawn wire (HDT) is lower, is difficult to use in and requires high occasion to resistance toheat.When PLLA and PDLA is blended, stereoscopic composite crystallization can be formed, its fusing point up to 230 DEG C, than the homogeneity crystallization height about 50 DEG C of independent PLLA or PDLA.Compared with independent PLLA or PDLA material, PLA Stereocomplex crystalline material has solvent resistant, the resistant to hydrolysis performance of high-melting-point, high strength, high-modulus and excellence, and its over-all properties is similar to the engineering plastics such as PET, nylon.Therefore, Stereocomplex crystallization is the effective way improving PLA over-all properties, and to widening, its industrial application is most important.
But the preparation of high heat-resisting PLA stereoscopic composite material is a difficult point.In PLLA/PDLA co-mixing system, there is the competition of homojunction crystallization and Stereocomplex crystallization.Simultaneously, PLLA and PDLA of suitability for industrialized production and laboratory synthesis is linear structure substantially, when linear PLL A and PDLA molecular weight larger time (weight-average molecular weight >40kg/mol), the main homogeneity crystallization forming PLLA or PDLA of low melting point in usual isothermal, non-isothermal melting behavior crystallization and cold crystallization process, the crystallization of more difficult formation dystectic PLLA/PDLA Stereocomplex.But mechanical property and the workability of lower molecular weight PLLA or PDLA (weight-average molecular weight <40kg/mol) are poor, and matter is crisp, is difficult to film forming, can not be directly used as plastics and use.Therefore, promote that the stereoscopic composite material of the Stereocomplex crystallization of high molecular (molecular weight >80kDa) PLA and preparation high molecular is significant to the over-all properties improving PLA.So, key prepared by high molecular PLA stereoscopic composite material how promotes the Stereocomplex crystallization between PLLA and PDLA by molecular chain structure design, processing conditions optimization, suppress the homojunction crystallization of PLLA or PDLA self, and how to improve the speed of Stereocomplex crystallization.
Polymer molecular chain topological framework is the important factor affecting its crystalline texture and crystal formation.Yui etc. (Makromol.Chem., 1990,191,481) once reported utilize block copolymerization to make PLLA with PDLA chain is intersegmental is connected by covalent linkage, being separated between crystallization neutral body isomery chain can be avoided, thus effectively promote its Stereocomplex crystallization.Compared with linear polymer, the hyper-branched chain structure such as star or pectination not only can significantly improve the molecular weight of polymkeric substance, and can improve the interaction between PLLA and PDLA segment, thus is expected to the degree and the speed that improve its Stereocomplex crystallization.Compared with PLLA and PDLA Stereoblock polymers, hyper-branched PLLA and PDLA more easily synthesizes, more easily adopt blended method to prepare stereoscopic composite material, work in-process also facilitates the degree, crystallization velocity and the material property that regulate and control its Stereocomplex crystallization by changing crystallization condition.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of preparation method of poly-lactic acid in high molecular weight material of easy Stereocomplex crystallization.
For solving the problems of the technologies described above, solution of the present invention is:
There is provided a kind of preparation method of poly-lactic acid in high molecular weight material of easy Stereocomplex crystallization, the concrete steps of the method are: component A and B component are adopted solution blending or melt blending, namely obtains described poly-lactic acid in high molecular weight material; Wherein, component A is linear PLLA (l-PLLA) or hyper-branched PLLA (b-PLLA), and optical purity is greater than 95%; B component is hyper-branched poly-dextrolactic acid (b-PDLA), and optical purity is greater than 95%; Component A is 1/1 ~ 9/1 with the mixing quality ratio of B component.
In the present invention, described solution blending refers to: get component A and B component is dissolved in easy volatile solvent, makes the concentration of polymers soln be 50g/L; After being uniformly mixed, polymers soln being watered and casts from tetrafluoroethylene culture dish; At room temperature make easy volatile solvent volatilize completely, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C, namely obtain poly-lactic acid in high molecular weight material.
In the present invention, described easy volatile solvent is methylene dichloride or chloroform.
In the present invention, described melt blending refers to: get component A and B component adds in single screw extrusion machine or twin screw extruder, mixing 3min at 210 DEG C, then extrudes pelletizing, namely obtains poly-lactic acid in high molecular weight material.
In the present invention, described hyper-branched PLLA has following structure:
In formula, n is the mean polymerisation degree of cellulose acetate main chain, and x is the mean polymerisation degree of wall scroll poly(lactic acid) side chain.
In the present invention, described hyper-branched poly-dextrolactic acid has following structure:
In formula, n is the mean polymerisation degree of cellulose acetate main chain, and x is the mean polymerisation degree of wall scroll poly(lactic acid) side chain.
Compared with prior art, the invention has the beneficial effects as follows:
1, prepared in the present invention high molecular PLA stereoscopic composite material fusing point, higher than 210 DEG C, effectively improves the resistance toheat of usual PLA, also can improve its solvent resistance and degradation resistance simultaneously.
2, the raw material of material prepared by the present invention all carrys out authigenic material renewable resources, can be degradable after using, and environmental protection, has good biocompatibility simultaneously.
3, high molecular PLA stereoscopic composite material of the present invention adopts blending method preparation, and the course of processing is simple, and cost is low, is easy to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the DSC heating curve (10 DEG C/min) of the melting quench sample of embodiment 3,8 and comparative example 1.
Fig. 2 is embodiment 3 and the isothermal melting crystallization DSC curve of comparative example 1 sample under 140 DEG C of conditions.
Fig. 3 is embodiment 3 and the DSC heating curve of comparative example 1 sample under 140 DEG C of conditions after isothermal fusion-crystallization (10 DEG C/min).
The WAXD curve of Fig. 4 for surveying after embodiment 2 and the isothermal melting crystallization of comparative example 1 sample under 140 DEG C of conditions.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
The present invention prepare used reagent and medicine as follows: linear PLLA (l-PLLA) produced purchased from Japanese Shimazu company, and its number-average molecular weight is 116kg/mol, and weight-average molecular weight is 198kg/mol.Cellulose acetate available from Sigma, its molecular weight is about 30kg/mol, and acetyl content is about 40wt%, the average substitution degree about 2.2 of ethanoyl.L-rac-Lactide and D-rac-Lactide purchased from Purao AS, recrystallization after acetic acid ethyl dissolution, for subsequent use; Octoate catalyst Ya Xi available from Sigma; Lauryl alcohol is purchased from Amethyst Chemical company.
Comparative example of the present invention linear poly-dextrolactic acid (l-PDLA) used is made by oneself by the ring-opening polymerization of D-rac-Lactide, and its number-average molecular weight is 190kg/mol, and weight-average molecular weight is 298kg/mol.Concrete preparation process is as follows: will add in flask after 50g D-rac-Lactide (purchased from Purao AS), 0.08g lauryl alcohol and the drying of 0.05g stannous octoate, argon shield, reacts 5h, obtain polymeric articles at 130 DEG C.
The present invention's hyper-branched PLLA used (b-PLLA) and hyper-branched poly-dextrolactic acid (b-PDLA) reference (Teramoto etc.; Polymer; 2003; 44; 2701) prepare; take cellulose acetate as macromole evocating agent; rac-Lactide is monomer, stannous octoate is catalyzer; concrete preparation process is as follows: be added in Xi Dingke pipe by a certain amount of cellulose acetate, L-rac-Lactide or D-rac-Lactide, stannous octoate; stannous octoate amount used is the 0.8wt% of lactide monomer quality; argon shield, reacts 5h at 130 DEG C.Dissolved in trichloromethane by the polymeric articles obtained, the unreacted rac-Lactide of dehydrated alcohol precipitation removing, filter, drying obtains polymkeric substance.By changing the mass ratio of cellulose acetate and rac-Lactide, prepare the graft copolymer with different molecular weight.Molecular weight, the molecular weight distributing index (PDI) of polymkeric substance are measured by gel permeation chromatograph (GPC).Preparation condition and the molecular weight of b-PLLA and b-PDLA used herein list in table 1.
The constitutional features of table 1:b-PLLA and b-PDLA
In polymer name b-PLLA-340k, b represents hyper-branched, and 340k represents weight-average molecular weight.
Molecular weight is tested: molecular weight of copolymer distribution adopts Waters gel permeation chromatograph to measure, and probe temperature is 30 DEG C, and moving phase is tetrahydrofuran (THF), and standard model is monodisperse polystyrene.
Embodiment 1 ~ 5
The component A of certain mass and B component are dissolved in chloroform, wherein A and B component are respectively b-PLLA and b-PDLA, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then make easy volatile solvent volatilize completely under room temperature, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C.
Embodiment 6 ~ 10
The component A of certain mass and B component are dissolved in chloroform, wherein A and B component are respectively l-PLLA and b-PDLA, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then make easy volatile solvent volatilize completely under room temperature, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C.
Embodiment 11
The component A of certain mass and B component are added in extruder double-screw forcing machine, wherein A and B component are respectively b-PLLA and b-PDLA, mixing 3min at 210 DEG C, then extrude pelletizing.
Comparative example 1 ~ 3
Certain mass l-PLLA and l-PDLA is dissolved in chloroform, the concentration of polymers soln is 50g/L, after being uniformly mixed, polymers soln is watered and casts from tetrafluoroethylene culture dish, then make easy volatile solvent volatilize completely under room temperature, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C.
The test of crystallization behavior: use DSC test, nitrogen atmosphere.In the test of non-isothermal cold crystallization, sample from room temperature to 250 DEG C with 50 DEG C/min, keeps 2min to eliminate thermal history, is then cooled to 0 DEG C with 100 DEG C/min, after keeping 3min, then is warming up to 250 DEG C with 10 DEG C/min at 0 DEG C.In isothermal melting crystallization test, sample with 50 DEG C/min from room temperature to 250 DEG C, keep 2min to eliminate thermal history, then with 100 DEG C/min fast cooling to institute's probe temperature, keep for some time to make the complete crystallization of polymkeric substance, then be warming up to 250 DEG C of test melting behaviors with 10 DEG C/min.
Kinetics of crystallization and Thermal Parameter calculate: in the 10 DEG C/min temperature-rise period after non-isothermal cold crystallization, and the peak temperature of cold crystallization exothermic peak is cold crystallization temperature (T
cc), integral area is cold crystallization enthalpy (Δ H
cc); Endotherm(ic)peak between 140 DEG C to 180 DEG C is the melting peak of PLLA, PDLA homogeneity crystallization, and peak temperature is homogeneity crystalline melt point (T
m, hc), integral area is homogeneity crystallization melting enthalpy (Δ H
m, hc).Endotherm(ic)peak between 180 DEG C to 240 DEG C is the melting peak of PLLA/PDLA blend Stereocomplex crystallization, and peak temperature is Stereocomplex crystalline melt point (T
m, sc), integral area is Stereocomplex crystallization enthalpy (Δ H
m, sc).Relative fractions (the f of Stereocomplex crystallization
sc) by formula f
sc=Δ H
m, sc/ (Δ H
m, sc+ Δ H
m, hc) calculate.Based on the data of isothermal melting crystallization, flexible chain (t
0.5) obtained by Avrami Equation for Calculating, concrete grammar reference literature ACS Applied Materials & Interfaces, 2009, Isosorbide-5-Nitrae 02.
The Thermal Parameter of melting quench sample in non-isothermal cold crystallization and melting process of embodiment 1 ~ 11 and comparative example 1 ~ 3 is as shown in table 2, and wherein temperature rise rate is 10 DEG C/min.
Table 2: the Thermal Parameter of melting quench sample in non-isothermal cold crystallization and melting process of embodiment 1 ~ 11 and comparative example 1 ~ 3
From table 1 and Fig. 1: in comparative example 1, when A and B component are linear structure, melting enthalpy and the relative content thereof of Stereocomplex crystallization are less, and the main homogeneity crystallization forming low melting point in co-mixing system is described.Compared with comparative example 1, the content of the Stereocomplex crystallization in embodiment 1 ~ 3 and 6 ~ 8 sample enlarges markedly.When A and B component are respectively b-PLLA and b-PDLA (embodiment 1 ~ 3), in temperature-rise period, be fully formed dystectic Stereocomplex crystallization, and along with the increase of molecular weight, Stereocomplex crystallization Crystallization degree increases.When A and B component are respectively l-PLLA and b-PDLA, occur the melting peak of homogeneity crystallization and Stereocomplex crystallization at temperature-rise period, but compared with comparative example 1, melting enthalpy and the relative content of Stereocomplex crystallization obviously increase.Comparing embodiment 3 and embodiment 11 known, blend method does not make significant difference to crystallization behavior, adopt solution blending substantially identical with b-PLLA with the b-PDLA blend Thermal Parameter of melt blending.Comparing embodiment 4,5,9,10 and comparative example 2,3 known, for the co-mixing system of the mass ratio such as PLLA, PDLA be non-, the use with the PLA of hyper-branched structure still can improve crystallization velocity and the Stereocomplex crystalline content of co-mixing system.
Table 3: kinetics in 140 DEG C of isothermal melting crystallizations of embodiment 1 ~ 3,6 ~ 8 and comparative example 1 sample and Thermal Parameter
From table 2 and Fig. 2,3, when A and B component are respectively b-PLLA and b-PDLA, only form dystectic Stereocomplex crystallization at isothermal melting crystallisation process.Along with the increase of molecular weight, t
0.5remarkable shortening, crystallization velocity is accelerated.When A and B component are respectively l-PLLA and b-PDLA, in isothermal crystal, define homogeneity crystallization and Stereocomplex crystallization, but compared with comparative example 1, the content of Stereocomplex crystallization enlarges markedly simultaneously.In addition, for embodiment 1 ~ 3 and 6 ~ 8 sample, its t
0.5significantly lower than the result of comparative example 1.The structure of these non-isothermals and isothermal crystal demonstrates and adopts the PLA with hyper-branched structure as blend components, the content of high-melting-point Stereocomplex crystallization in high molecular PLLA/PDLA co-mixing system can be significantly improved, also can improve the crystallization velocity of blend simultaneously.
For confirming in the present invention that PLA that preparation has a hyper-branched structure is conducive to the generation of Stereocomplex crystallization further, wide-angle X ray diffractor (WAXD) being carried out to 140 DEG C of isothermal melting crystallized sample of example 2 and comparative example 1 and tests.As shown in Figure 4: embodiment 2 only presents the diffraction peak of the Stereocomplex crystallization of PLA, and occurs the homogeneity crystallization of PLA and the diffraction peak of Stereocomplex crystallization in comparative example 1 simultaneously, and the diffraction peak intensity of homogeneity crystallization is apparently higher than Stereocomplex crystallization.In Fig. 4, sc represents Stereocomplex crystallization, and hc represents homogeneity crystallization.
Utilize dynamic properties tester analysis of material storage modulus at different temperatures.By blend isothermal cold crystallization under 100 DEG C of conditions, be then cut into 50 × 6 × 0.5mm
3thin slice, carry out dynamic properties test.Test condition is as follows: the frequency of stress is 5Hz, and Range of measuring temp is-30 ~ 250 DEG C, and temperature rise rate is 3 DEG C/min.Dynamic properties test result finds, the storage modulus of embodiment 3 and 8 200 DEG C time still can reach 1.09MPa and 0.36MPa, and now l-PLLA melting completely, illustrate that Stereocomplex crystallization can significantly improve the resistance toheat of PLA.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, a lot of distortion can also be had.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (6)
1. a preparation method for the poly-lactic acid in high molecular weight material of easy Stereocomplex crystallization, is characterized in that, the concrete steps of the method are: component A and B component are adopted solution blending or melt blending, namely obtains described poly-lactic acid in high molecular weight material; Wherein, component A is linear PLLA (l-PLLA) or hyper-branched PLLA (b-PLLA), and optical purity is greater than 95%; B component is hyper-branched poly-dextrolactic acid (b-PDLA), and optical purity is greater than 95%; Component A is 1/1 ~ 9/1 with the mixing quality ratio of B component.
2. method according to claim 1, is characterized in that, described solution blending refers to:
Get component A and B component is dissolved in easy volatile solvent, make the concentration of polymers soln be 50g/L; After being uniformly mixed, polymers soln being watered and casts from tetrafluoroethylene culture dish; At room temperature make easy volatile solvent volatilize completely, then tetrafluoroethylene culture dish is put into the dry 6h of vacuum drying oven of 60 DEG C, namely obtain poly-lactic acid in high molecular weight material.
3. method according to claim 2, is characterized in that, described easy volatile solvent is methylene dichloride or chloroform.
4. method according to claim 1, is characterized in that, described melt blending refers to:
Get component A and B component adds in single screw extrusion machine or twin screw extruder, mixing 3min at 210 DEG C, then extrude pelletizing, namely obtain poly-lactic acid in high molecular weight material.
5. according to the method described in Claims 1-4 any one, it is characterized in that, described hyper-branched PLLA has following structure:
In formula, n is the mean polymerisation degree of cellulose acetate main chain, and x is the mean polymerisation degree of wall scroll poly(lactic acid) side chain.
6. according to the method described in Claims 1-4 any one, it is characterized in that, described hyper-branched poly-dextrolactic acid has following structure:
In formula, n is the mean polymerisation degree of cellulose acetate main chain, and x is the mean polymerisation degree of wall scroll poly(lactic acid) side chain.
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| CN104877317A (en) * | 2015-05-29 | 2015-09-02 | 江南大学 | Preparation method of full-bio-based composite material capable of being rapidly composited stereoscopically after melting |
| CN104927322A (en) * | 2015-05-29 | 2015-09-23 | 江南大学 | Method for rapidly forming polylactic acid stereocomplex |
| CN105368023A (en) * | 2015-11-18 | 2016-03-02 | 浙江大学 | Easy stereo-complex crystal supramolecular stereoblock polylactic acid and preparation method thereof |
| CN105463624A (en) * | 2015-12-28 | 2016-04-06 | 上海新宁生物材料有限公司 | Preparation method of polylactic acid stereo-compound with high stereo-rate |
| CN105506776A (en) * | 2016-02-03 | 2016-04-20 | 北京服装学院 | Modified polylactic acid fiber and preparation method thereof |
| CN105542411A (en) * | 2016-01-22 | 2016-05-04 | 浙江大学 | Preparation method for polylactic acid material capable of easily achieving stereocomplex crystallization |
| CN106700098A (en) * | 2016-12-15 | 2017-05-24 | 浙江大学 | Preparation method of biodegradable supermolecule polylactic acid microspheres |
| CN107325302A (en) * | 2017-07-13 | 2017-11-07 | 东华大学 | A kind of preparation method of polylactic acid stereoscopic composite |
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| CN113980442A (en) * | 2021-11-26 | 2022-01-28 | 江苏科技大学 | Rapid-crystallization all-dimensional composite crystalline polylactic acid material and preparation method thereof |
| CN115124822A (en) * | 2022-06-02 | 2022-09-30 | 南通大学 | Degradation-controllable polylactic acid material and preparation method and application thereof |
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| CN104877317A (en) * | 2015-05-29 | 2015-09-02 | 江南大学 | Preparation method of full-bio-based composite material capable of being rapidly composited stereoscopically after melting |
| CN105368023A (en) * | 2015-11-18 | 2016-03-02 | 浙江大学 | Easy stereo-complex crystal supramolecular stereoblock polylactic acid and preparation method thereof |
| CN105463624A (en) * | 2015-12-28 | 2016-04-06 | 上海新宁生物材料有限公司 | Preparation method of polylactic acid stereo-compound with high stereo-rate |
| 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 |
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| CN105542411B (en) * | 2016-01-22 | 2017-12-01 | 浙江大学 | The preparation method of the poly-lactic acid material of easy Stereocomplex crystallization |
| CN105506776A (en) * | 2016-02-03 | 2016-04-20 | 北京服装学院 | Modified polylactic acid fiber and preparation method thereof |
| CN105506776B (en) * | 2016-02-03 | 2019-01-22 | 北京服装学院 | A kind of modified polylactic acid fiber and preparation method thereof |
| CN106700098A (en) * | 2016-12-15 | 2017-05-24 | 浙江大学 | Preparation method of biodegradable supermolecule polylactic acid microspheres |
| CN107325302A (en) * | 2017-07-13 | 2017-11-07 | 东华大学 | A kind of preparation method of polylactic acid stereoscopic composite |
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