CN104650548B - The easily preparation method of the poly-lactic acid in high molecular weight material of Stereocomplex crystallization - Google Patents
The easily preparation method of the poly-lactic acid in high molecular weight material of Stereocomplex crystallization Download PDFInfo
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Abstract
The present invention relates to degradable high polymer material modification technology, it is desirable to provide the preparation method of the poly-lactic acid in high molecular weight material of a kind of easy Stereocomplex crystallization.The method is to use solution blending or melt blending to obtain poly-lactic acid in high molecular weight material with linear Poly-L-lactic acid or hyper-branched Poly-L-lactic acid two component hyper-branched poly-L-lactic acid；The optical purity of two components is more than 95%.High molecular PLA stereoscopic composite material fusing point prepared in the present invention, higher than 210 DEG C, is effectively increased the heat resistance of usual PLA, also can improve its solvent resistance and degradation resistance simultaneously.Raw material is all from biomass Renewable resource, can be degradable after using, and environmental protection has good biocompatibility simultaneously.Prepared by employing blending method, the course of processing is simple, low cost, it is easy to large-scale industrial production.
Description
Technical field
The present invention is about bio-based, Biodegradable polymer material technical field of modification, particularly to easy Stereocomplex
The preparation method of heat-resisting poly-lactic acid in high molecular weight material crystallization, high.
Background technology
Polylactic acid (PLA) has excellent biodegradability, biocompatibility, mechanical mechanics property, machinability
Deng, it is to substitute a kind of good of conventional petroleum base polymeric material to select.Owing to the monomer of PLA has enantiomerically,
Therefore PLA has two kinds of enantiomer-specific structures, i.e. Poly-L-lactic acid (PLLA) and poly-L-lactic acid (PDLA), wherein PLLA
The most common.The fusing point of PLLA is about 170 DEG C, but owing to its crystalline rate is relatively slow, in the normal melt course of processing
PLLA crystallizes hardly or degree of crystallinity is extremely low, and therefore its heat distortion temperature (HDT) is relatively low, it is difficult to for thermostability
High occasion can be required.When PLLA and PDLA is blended, can form stereoscopic composite crystallization, its fusing point is up to 230 DEG C,
Homogeneity crystallization than independent PLLA or PDLA is high about 50 DEG C.Compared with single PLLA or PDLA material, PLA
Stereocomplex crystalline material has the solvent resistant of high-melting-point, high intensity, high-modulus and excellence, resistant to hydrolysis performance, and it is comprehensive
Performance is similar to the engineering plastics such as PET, nylon.Therefore, Stereocomplex crystallization is to improve having of PLA combination property
Effect approach, 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, deposit
In homojunction crystallization and the competition of Stereocomplex crystallization.Meanwhile, industrialized production and laboratory synthesis PLLA and
PDLA is linear structure substantially, and when linear PLL A and PDLA molecular weight are bigger (weight average molecular weight > 40
Kg/mol), usual isothermal, non-isothermal melting behavior crystallization and cold crystallization process in primarily form low melting point PLLA or
The homogeneity crystallization of PDLA, it is more difficult to form the crystallization of dystectic PLLA/PDLA Stereocomplex.But low-molecular-weight PLLA
Or the mechanical performance of PDLA (weight average molecular weight < 40kg/mol) and machinability poor, matter is crisp, it is difficult to film forming, it is impossible to
It is directly used as plastics to use.Therefore, promote high molecular (molecular weight > 80kDa) PLA Stereocomplex crystallization and
The stereoscopic composite material of preparation high molecular is significant to the combination property improving PLA.So, macromolecule
Prepared by amount PLA stereoscopic composite material it is crucial that how to be promoted by molecular chain structure design, processing conditions optimization
Stereocomplex crystallization between PLLA and PDLA, the homojunction crystallization of suppression PLLA or PDLA self, and
How to improve the speed of Stereocomplex crystallization.
Polymer molecular chain topological structure is the key factor affecting its crystalline texture with crystal formation.(the Makromol. such as Yui
Chem., 1990,191,481) once report utilize block copolymerization to make PLLA with PDLA chain is intersegmental is connected by covalent bond,
Can avoid crystallizing being separated between neutral body isomery chain, thus effectively facilitate its Stereocomplex crystallization.With linear polymerization
Thing is compared, and the hyper-branched chain structure such as star or pectination is not only remarkably improved the molecular weight of polymer, and can improve PLLA
And the interaction between PDLA segment, thus it is expected to improve degree and the speed of its Stereocomplex crystallization.With PLLA
Compared with PDLA Stereoblock polymers, hyper-branched PLLA and PDLA is relatively easily-synthesized, and is more easy to use the side being blended
Method prepares stereoscopic composite material, and work in-process is also convenient for regulating and controlling its Stereocomplex crystallization by change crystallization condition
Degree, crystallization rate and material property.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, it is provided that a kind of easily Stereocomplex crystallization
The preparation method of poly-lactic acid in high molecular weight material.
For solving above-mentioned technical problem, the solution of the present invention is:
The preparation method of the poly-lactic acid in high molecular weight material of a kind of easy Stereocomplex crystallization, the concrete steps of the method are provided
It is: component A and component B are used solution blending or melt blending, i.e. obtains described poly-lactic acid in high molecular weight material；
Wherein, component A is linear Poly-L-lactic acid (l-PLLA) or hyper-branched Poly-L-lactic acid (b-PLLA), optical voidness
Degree is more than 95%；Component B is hyper-branched poly-L-lactic acid (b-PDLA), and optical purity is more than 95%；Component A with
The mixing quality ratio of component B is 1/1～9/1.
In the present invention, described solution blending refers to: take component A and component B is dissolved in effumability solvent, make to gather
The concentration of polymer solution is 50g/L；After being uniformly mixed, polymer solution is watered and casts from politef culture dish；
At room temperature make effumability solvent volatilize completely, then politef culture dish is put in the vacuum drying oven of 60 DEG C dry
Dry 6h, i.e. obtains poly-lactic acid in high molecular weight material.
In the present invention, described effumability solvent is dichloromethane or chloroform.
In the present invention, described melt blending refers to: take component A and component B adds single screw extrusion machine or double spiral shell
In bar extruder, mixing 3min at 210 DEG C, then extrude pelletizing, i.e. obtain poly-lactic acid in high molecular weight material.
In the present invention, described hyper-branched Poly-L-lactic acid has a structure that
In formula, n is the average degree of polymerization of cellulose acetate main chain, and x is the average degree of polymerization of wall scroll polylactic acid side chain.
In the present invention, described hyper-branched poly-L-lactic acid has a structure that
In formula, n is the average degree of polymerization of cellulose acetate main chain, and x is the average degree of polymerization of wall scroll polylactic acid side chain.
Compared with prior art, the invention has the beneficial effects as follows:
1, high molecular PLA stereoscopic composite material fusing point prepared in the present invention is higher than 210 DEG C, is effectively increased
The generally heat resistance of PLA, also can improve its solvent resistance and degradation resistance simultaneously.
2, the raw material of material prepared by the present invention is all from biomass Renewable resource, can be degradable after using, green
Environmental protection, has good biocompatibility simultaneously.
3, high molecular PLA stereoscopic composite material of the present invention uses blending method to prepare, and the course of processing is simple, becomes
This is low, it is easy to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the DSC heating curve (10 DEG C/min) of embodiment 3,8 and the melted qtenched sample of comparative example 1.
Fig. 2 is that embodiment 3 crystallizes DSC curve with comparative example 1 sample isothermal melting under the conditions of 140 DEG C.
Fig. 3 is embodiment 3 and comparative example 1 sample DSC heating curve after isothermal melting crystallization under the conditions of 140 DEG C
(10℃/min)。
The WAXD that Fig. 4 is surveyed after crystallizing with comparative example 1 sample isothermal melting under the conditions of 140 DEG C by embodiment 2 is bent
Line.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.The following examples can make this
The professional and technical personnel of specialty is more fully understood the present invention, but limits the present invention never in any form.
It is as follows with medicine that the present invention prepares used reagent: linear Poly-L-lactic acid (l-PLLA) is purchased from Japan Shimazu
Company is produced, and its number-average molecular weight is 116kg/mol, and weight average molecular weight is 198kg/mol.Cellulose acetate is purchased from
Sigma company, its molecular weight is about 30kg/mol, and acetyl content about 40wt%, the average substitution degree of acetyl group is about
2.2.L-lactide and D-lactide purchased from Purao AS, recrystallization after acetic acid ethyl dissolution, standby；Catalyst
Stannous octoate is purchased from Sigma company；Lauryl alcohol is purchased from Amethyst Chemical company.
Linear poly-L-lactic acid (l-PDLA) used by comparative example of the present invention is made by oneself by the ring-opening polymerisation of D-lactide, its
Number-average molecular weight is 190kg/mol, and weight average molecular weight is 298kg/mol.Concrete preparation process is as follows: by 50g D-third
Lactide (purchased from Purao AS), 0.08g lauryl alcohol and 0.05g stannous octoate add in flask after drying, argon shield,
At 130 DEG C, react 5h, obtain polymeric articles.
Hyper-branched Poly-L-lactic acid (b-PLLA) used by the present invention and hyper-branched poly-L-lactic acid (b-PDLA) are with reference to literary composition
Offering (Teramoto etc., Polymer, 2003,44,2701) to prepare, with cellulose acetate as macromole evocating agent, third hands over
Ester be monomer, stannous octoate be catalyst, concrete preparation process is as follows: by a certain amount of cellulose acetate, L-lactide
Or D-lactide, stannous octoate add to the pipe of uncommon Dinke, stannous octoate amount used is the 0.8 of lactide monomer quality
Wt%, argon shield, at 130 DEG C, react 5h.The polymeric articles obtained is dissolved in chloroform, anhydrous second
Alcohol precipitation removes unreacted lactide, filters, is dried to obtain polymer.By changing cellulose acetate and lactide
Mass ratio, is prepared for the graft copolymer with different molecular weight.The molecular weight of polymer, molecular weight distributing index (PDI)
Measured by chromatograph of gel permeation (GPC).The preparation condition of b-PLLA and b-PDLA used herein and molecule
Amount is listed in table 1.
The architectural feature 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 uses Waters chromatograph of gel permeation to measure, and test temperature is 30 DEG C,
Flowing is oxolane mutually, and standard sample is monodisperse polystyrene.
Embodiment 1～5
Component A and the B component of certain mass are dissolved in chloroform, wherein A and B component be respectively b-PLLA and
B-PDLA, the concentration of polymer solution is 50g/L, after being uniformly mixed, is watered by polymer solution and casts from polytetrafluoroethyl-ne
In alkene culture dish, then make effumability solvent volatilize completely under room temperature, then politef culture dish is put into 60 DEG C
Vacuum drying oven is dried 6h.
Embodiment 6～10
Component A and the B component of certain mass are dissolved in chloroform, wherein A and B component be respectively l-PLLA and
B-PDLA, the concentration of polymer solution is 50g/L, after being uniformly mixed, is watered by polymer solution and casts from polytetrafluoroethyl-ne
In alkene culture dish, then make effumability solvent volatilize completely under room temperature, then politef culture dish is put into 60 DEG C
Vacuum drying oven is dried 6h.
Embodiment 11
Adding in extruder double-screw extruder by component A and the B component of certain mass, wherein A and B component are respectively
For b-PLLA and b-PDLA, mixing 3min at 210 DEG C, then extrude pelletizing.
Comparative example 1～3
Being dissolved in chloroform by certain mass l-PLLA and l-PDLA, the concentration of polymer solution is 50g/L, stirring mixing
After Jun Yun, polymer solution is watered and casts from politef culture dish, then under room temperature, make effumability solvent wave completely
Send out, then politef culture dish is put into dry 6h in the vacuum drying oven of 60 DEG C.
The test of crystallization behavior: use DSC test, nitrogen atmosphere.In non-isothermal cold crystallization is tested, sample is with 50 DEG C
/ min, from room temperature to 250 DEG C, keeps 2min to eliminate thermal history, is then cooled to 0 DEG C with 100 DEG C/min,
After keeping 3min at 0 DEG C, then it is warming up to 250 DEG C with 10 DEG C/min.In isothermal melting crystallization test, sample
With 50 DEG C/min from room temperature to 250 DEG C, 2min is to eliminate thermal history in holding, then quick with 100 DEG C/min
It is cooled to tested temperature, keeps a period of time to make polymer be fully crystallized, then be warming up to 250 DEG C of surveys with 10 DEG C/min
Examination melting behavior.
Crystallization kinetics calculates with Thermal Parameter: in the 10 DEG C/min temperature-rise period after non-isothermal cold crystallization, cold
The peak temperature of crystalline exotherm peak is cold crystallization temperature (Tcc), integral area is cold crystallization enthalpy (Δ Hcc)；140 DEG C extremely
Endothermic peak between 180 DEG C is the melting peak of PLLA, PDLA homogeneity crystallization, and peak temperature is homogeneity crystalline melt point (Tm,hc),
Integral area is that homogeneity crystallizes melting enthalpy (Δ Hm,hc).Endothermic peak between 180 DEG C to 240 DEG C is that PLLA/PDLA is blended
The melting peak of thing Stereocomplex crystallization, peak temperature is Stereocomplex crystalline melt point (Tm,sc), integral area is multiple for vertical structure
Close crystallization enthalpy (Δ Hm,sc).Relative fractions (the f of Stereocomplex crystallizationsc) by formula fsc=Δ Hm,sc/(ΔHm,sc+ΔHm,hc)
It is calculated.Data based on isothermal melting crystallization, flexible chain (t0.5) obtained by Avrami Equation for Calculating, tool
Body method reference literature ACS Applied Materials&Interfaces, 2009,1,402.
Embodiment 1～11 and the melted qtenched sample of comparative example 1～3 hot property in non-isothermal cold crystallization and melting process
Parameter is as shown in table 2, and wherein heating rate is 10 DEG C/min.
Table 2: the melted qtenched sample of embodiment 1～11 and comparative example 1～3 is in non-isothermal cold crystallization and melting process
Thermal Parameter
From table 1 and Fig. 1: in comparative example 1, when A and B component are linear structure, Stereocomplex is tied
Brilliant melting enthalpy and relative amount thereof are less, illustrate to primarily form in co-mixing system the homogeneity crystallization of low melting point.With comparative example
1 compares, and the content of the Stereocomplex crystallization in embodiment 1～3 and 6～8 sample significantly increases.When A and B component are divided
Not Wei b-PLLA and b-PDLA time (embodiment 1～3), temperature-rise period is formed dystectic Stereocomplex completely
Crystallization, and along with the increase of molecular weight, Stereocomplex crystallization Crystallization degree increases.When A and B component are respectively l-PLLA
During with b-PDLA, at temperature-rise period, homogeneity crystallization and the melting peak of Stereocomplex crystallization occur, but compared with comparative example 1,
Melting enthalpy and the relative amount of Stereocomplex crystallization significantly increase.Comparing embodiment 3 and embodiment 11 understand, and side is blended
Crystallization behavior is not made significant difference by method, b-PLLA and the b-PDLA blend using solution blending and melt blending is hot
Energy parameter is essentially identical.Comparing embodiment 4,5,9,10 and comparative example 2,3 understand, non-for PLLA, PDLA
Deng the co-mixing system of mass ratio, the use of the PLA with hyper-branched structure still can improve the crystallization rate of co-mixing system
With Stereocomplex crystalline content.
Table 3: kinetics in 140 DEG C of isothermal meltings 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, at isothermal melting
Crystallization process only forms the crystallization of dystectic Stereocomplex.Along with the increase of molecular weight, t0.5Notable shortening, crystallization rate adds
Hurry up.When A and B component are respectively l-PLLA and b-PDLA, isothermal crystal concurrently forms homogeneity crystallization with vertical
Structure compound crystal, but compared with comparative example 1, the content of Stereocomplex crystallization significantly increases.It addition, for embodiment 1～3
With 6～8 samples, its t0.5It is substantially less than the result of comparative example 1.The structure of these non-isothermals and isothermal crystal demonstrates adopts
With there is the PLA of hyper-branched structure as blend components, it is remarkably improved in high molecular PLLA/PDLA co-mixing system
The content of high-melting-point Stereocomplex crystallization, also can improve the crystallization rate of blend simultaneously.
For further confirming that in the present invention, preparation has the generation that the PLA of hyper-branched structure is conducive to Stereocomplex to crystallize,
140 DEG C of isothermal melting crystallized sample of example 2 with comparative example 1 are carried out wide-angle X ray diffractor (WAXD) survey
Examination.As shown in Figure 4: embodiment 2 only presents the diffraction maximum of the Stereocomplex crystallization of PLA, and in comparative example 1 simultaneously
Homogeneity crystallization and the diffraction maximum of Stereocomplex crystallization of PLA occur, and the diffraction peak intensity of homogeneity crystallization is apparently higher than vertical
Structure compound crystal.In Fig. 4, sc represents Stereocomplex crystallization, and hc represents homogeneity crystallization.
Utilize dynamic mechanical tester analysis of material storage modulus at different temperatures.By blend at 100 DEG C of bars
Isothermal cold crystallization under part, is then cut into 50 × 6 × 0.5mm3Thin slice, carry out dynamic mechanical test.Test strip
Part is as follows: the frequency of stress is 5Hz, and Range of measuring temp is-30～250 DEG C, and heating rate is 3 DEG C/min.Dynamically
Mechanical experimental results finds, the embodiment 3 and 8 storage modulus when 200 DEG C still up to 1.09MPa and
0.36MPa, and now l-PLLA is the most melted, illustrates that Stereocomplex crystallization is remarkably improved the heat-resisting of PLA
Performance.
It is only the specific embodiment of the present invention finally it should be noted that listed above.It is clear that the invention is not restricted to
Above example, it is also possible to have many variations.Those of ordinary skill in the art can from present disclosure directly
The all deformation derived or associate, are all considered as protection scope of the present invention.
Claims (4)
1. the preparation method of the poly-lactic acid in high molecular weight material of an easy Stereocomplex crystallization, it is characterised in that comprising the concrete steps that of the method: component A and component B are used solution blending or melt blending, i.e. obtains described poly-lactic acid in high molecular weight material；Wherein, component A is linear Poly-L-lactic acid (l-PLLA) or hyper-branched Poly-L-lactic acid (b-PLLA), and optical purity is more than 95%；Component B is hyper-branched poly-L-lactic acid (b-PDLA), and optical purity is more than 95%；Component A is 1/1～9/1 with the mixing quality ratio of component B；
Described hyper-branched Poly-L-lactic acid has a structure that
In formula, n is the average degree of polymerization of cellulose acetate main chain, and x is the average degree of polymerization of wall scroll polylactic acid side chain；
Described hyper-branched poly-L-lactic acid has a structure that
In formula, n is the average degree of polymerization of cellulose acetate main chain, and x is the average degree of polymerization of wall scroll polylactic acid side chain.
Method the most according to claim 1, it is characterised in that described solution blending refers to:
Taking component A and component B is dissolved in effumability solvent, the concentration making polymer solution is 50g/L；After being uniformly mixed, polymer solution is watered and casts from politef culture dish；At room temperature make effumability solvent volatilize completely, then politef culture dish is put into dry 6h in the vacuum drying oven of 60 DEG C, i.e. obtain poly-lactic acid in high molecular weight material.
Method the most according to claim 2, it is characterised in that described effumability solvent is dichloromethane or chloroform.
Method the most according to claim 1, it is characterised in that described melt blending refers to:
Take component A and component B adds in single screw extrusion machine or double screw extruder, mixing 3min at 210 DEG C, then extrude pelletizing, i.e. obtain poly-lactic acid in high molecular weight material.
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| CN104927322B (en) * | 2015-05-29 | 2016-08-24 | 江南大学 | A kind of method of quick formation polylactic acid stereoscopic composite |
| CN104877317B (en) * | 2015-05-29 | 2016-10-26 | 江南大学 | A kind of melted after can the preparation method of the quick full bio-based composite material of Stereocomplex |
| CN105368023B (en) * | 2015-11-18 | 2017-03-15 | 浙江大学 | Supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN106700098B (en) * | 2016-12-15 | 2019-02-22 | 浙江大学 | The preparation method of biodegradable supermolecule polylactic acid microsphere |
| CN107325302A (en) * | 2017-07-13 | 2017-11-07 | 东华大学 | A kind of preparation method of polylactic acid stereoscopic composite |
| CN112480621A (en) * | 2020-12-04 | 2021-03-12 | 惠州莹光塑胶颜料有限公司 | Environment-friendly plastic master batch and preparation method thereof |
| 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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| CN101891940A (en) * | 2009-05-21 | 2010-11-24 | 中国科学院化学研究所 | Modified polyactic acid and preparation method thereof |
| CN102634866A (en) * | 2012-04-25 | 2012-08-15 | 中国科学院宁波材料技术与工程研究所 | Self-enhanced polylactic acid fiber and preparation method thereof |
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