CN103087298B - Multi-arm block copolymer, preparation method and application of multi-arm block copolymer in improvement of mechanical property of poly-L-lactic acid thereof - Google Patents
Multi-arm block copolymer, preparation method and application of multi-arm block copolymer in improvement of mechanical property of poly-L-lactic acid thereof Download PDFInfo
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Abstract
The invention discloses a multi-arm block copolymer and a preparation method as well as an application of the multi-arm block copolymer. Each arm of the multi-arm block copolymer is structured by a soft section and a hard section, wherein the soft section is poly-dl-lactide, or polycaprolactone or a copolymer of the poly-dl-lactide and the polycaprolactone; the hard section is poly-dextrolactic acid; a stereo composite crystal is formed through the poly-dextrolactic acid and the poly-dl-lactide of the multi-arm block copolymer and plays a role of a physical cross-link point; a multi-arm block copolymer system is fused and blended with the poly-dl-lactide, then a blend is formed by injection molding and a certain constant-temperature annealing treatment is carried out, so that the breaking elongation of the poly-dl-lactide can be obviously increased; and the multi-arm block copolymer can play a role of accelerating crystallization in the process of isothermal crystallization and still can retains good degradation and transparence properties, so that the important application prospects of the multi-arm block copolymer in modification of the mechanical property of the poly-L-lactic acid are shown.
Description
Technical field
The present invention relates to a kind of multi-arm segmented copolymer, preparation method and improving the application in Poly-L-lactic acid mechanical property.
Background technology
Along with the minimizing day by day of petroleum resources, the source of conventional plastic becomes more and more difficult, causes its price constantly to promote, and plastic prod is difficult to again after discarding decompose under field conditions (factors), causes great pollution to environment.Poly(lactic acid), due to the food-based starch of monomer whose (as corn), does not rely on petroleum resources, and biodegradable, there is not white garbage problem, and this just greatly reduces the pollution of consumption to the energy and environment.In recent years poly(lactic acid) particularly Poly-L-lactic acid (PLLA) be expected to receive as the replacer of conventional plastic both at home and abroad study (Anderson K et al.Toughening polylactide.Polymer Reviews 2008 widely, 48,85-108).Poly-L-lactic acid has good biocompatibility, biodegradability and the excellent transparency, there is very high mechanical strength (can compare favourably with polystyrene) simultaneously, be with a wide range of applications in the field such as daily life and biological medicine.But its second-order transition temperature higher (about 60 DEG C), material fragility is large, and crystallization velocity is slow, thus extends the forming process time of goods, reduces production efficiency.These performance deficiencies of Poly-L-lactic acid are serious must limit its widespread use in practice.Therefore, it is the important topic faced at present that the performance how improving Poly-L-lactic acid also realizes extensively utilizing.
At present, both at home and abroad Poly-L-lactic acid modification is conducted extensive research, such as Poly-L-lactic acid and the reasonable polymkeric substance of snappiness are carried out graft copolymerization or block copolymerization (Carolyn L et al.Consequences ofpolylactide stereochemistry on the properties of polylactide-polymenthide-polylactidethermoplastic elastomers.Biomacromolecules 2009, 10, 2904-2911), although the performance of Poly-L-lactic acid can be improved to a certain extent, but because this chemical modification method need redesign the production technique of existing Poly-L-lactic acid, need higher cost and time.The method of employing physical modification is the method for comparatively simple possible.Such as Poly-L-lactic acid and another degradation material polycaprolactone (PCL) are carried out blended.But the key of blend method is the selection of additive.Such as, take polycaprolactone as polymeric additive, due to itself and Poly-L-lactic acid blended after there is phase separation, therefore consistency is poor, thus causes mechanical property not to be effectively improved.If can design new polymer additive, improve the consistency of itself and Poly-L-lactic acid, this can improve mechanical property and the processing characteristics of Poly-L-lactic acid acid.
Stereocomplex crystalline substance is the characteristic of poly(lactic acid).When Poly-L-lactic acid and dextrorotation poly(lactic acid) (PDLA) blended with certain proportion after, a kind of new crystal formation can be formed, be referred to as Stereocomplex crystalline substance (stereocomplex).Its fusing point is higher than fusing point about 50 DEG C (Yoshito Ikada KJ et al.Stereocomplex formation betweenenantiomeric poly (lactides) .Macromolecules 1987 of Poly-L-lactic acid, 20,904-906).Research shows, Stereocomplex crystalline substance has the mechanical property being better than Poly-L-lactic acid, such as elongation at break and tensile modulus all increase (H.Tsuji.Stereocomplex formation between enantiomeric poly (lactic acid) s.XI.Mechanicalproperties and morphology of solution-cast films.Macromolecules 1999,40,6699-6708).In recent years, a kind of block copolymer structure improving Poly-L-lactic acid mechanical property is proposed in the world, flexibility soft section is preferably introduced respectively in this segmented copolymer, and the hard section of dextrorotation poly(lactic acid) (PDLA) of Stereocomplex crystalline substance can be formed with Poly-L-lactic acid, in order to improve mechanical property (the Rathi SR et al.Effect of midblock onthe morphology and properties of blends of ABA triblock copolymers ofPDLA-mid-block-PDLA with PLLA.Polymer 2012 of Poly-L-lactic acid, 53, 3008-3016).Except the mechanical property improving Poly-L-lactic acid, there are some researches show, the existence of polylactic acid stereoscopic composite crystal under certain conditions also can as the nucleator of Poly-L-lactic acid, thus play the effect promoting its crystallization, so just can reduce the crystallization time of dlactic acid, thus enhance productivity.(Tsuji H et al.Isothermal and non-isothermal crystallizationbehavior of poly(L-lactic acid)：Effects of stereocomplex as nucleating agent.Polymer 2006，47，3826-3837)。
Compared with linear polymer, multiarm polymers has a lot of property, such as many terminal group, multifunction (Young Kweon Choi et al.Star-shaped poly (ether-ester) block copolymers:Synthesis, characterization, and their physical properties.Macromolecules 1998, 31, 8766-8774), and special crystallization and rheological property (Weizhong Yuan et al.Synthesis, characterization, and thermalproperties of dendrimer-star, block-comb copolymers by ring-opening polymerization andatom transfer radical polymerization.Journal of Polymer Science:Part A:PolymerChemistry, 2006, 44, 6575-6586).These performances of multiarm polymers can be used in improvement (the Rahul Bhardwaj et al.Modification of brittle polylactide by novel hyperbranchedpolymer-based nanostructures.Biomacromolecules 2007 to poly(lactic acid) performance, 8,2476-2484).If further from the chemical structure of each arm of multiarm polymers and the regulation and control of composition, be expected to design new additive system, in order to improve crystallization and the mechanical property of Poly-L-lactic acid.
Summary of the invention
The object of this invention is to provide a kind of multi-arm segmented copolymer and preparation method thereof.
The structural formula of multi-arm segmented copolymer provided by the present invention is such as formula shown in I:
(formula I)
Wherein, n is for being more than or equal to 0 and being less than or equal to 3 integers;
Each arm forms by soft section and hard section two blocks,
for soft section, it represents the homopolymer or multipolymer that are formed by following at least one monomer: caprolactone (CL) and meso-lactide (d, 1-LA);
for hard section, it represents dextrorotation poly(lactic acid).
The arm number of the segmented copolymer of multi-arm shown in formula I specifically can from 2 arms to 5 arms.
In each arm of multi-arm segmented copolymer described in formula I, the number-average molecular weight of soft section is 100 ~ 100,000, the number-average molecular weight of hard section is 700 ~ and, 600,000.
The method of the segmented copolymer of multi-arm shown in preparation formula I, comprises the steps:
With the polyvalent alcohol shown in formula II for initiator; under argon shield; cause 6-caprolactone monomer (CL) and/or meso-lactide monomer (d; 1-LA) carry out ring-opening polymerization; again using prepared product as macromole evocating agent; the ring-opening polymerization of further initiation dextrorotation lactide monomer (d-LA), obtains described multi-arm segmented copolymer.
(formula II)
In formula II, n be more than or equal to 0 and be less than or equal to 3 integer.
Described ring-opening polymerization is carried out under the katalysis of catalyzer, and described catalyzer specifically can be stannous octoate.
When the arm number of the multi-arm segmented copolymer prepared is 2 to 5 arm, the initiator adopted is respectively ethylene glycol, glycerine, erythritol and Xylitol, and its chemical structural formula is as follows:
Prepared multi-arm segmented copolymer specifically can be two-arm poly-(6-caprolactone-b-dextrorotation poly(lactic acid)) (2a-PCL-b-PDLA), two-arm poly-(PDLLA-b-dextrorotation poly(lactic acid)) (2a-PDLLA-b-PDLA), four arms poly-(PDLLA-b-dextrorotation poly(lactic acid)) (4a-PDLLA-b-PDLA) etc.
The structural formula of described polymer PC L, PLA is as follows:
Another object of the present invention is to provide the application of above-mentioned multi-arm segmented copolymer.
The application of multi-arm segmented copolymer provided by the present invention is that it is improving the application in Poly-L-lactic acid mechanical property.This multi-arm segmented copolymer and Poly-L-lactic acid blended after, have good improvement to the mechanical property of Poly-L-lactic acid, keep mechanics of materials intensity simultaneously basic, obviously can increase the elongation at break of Poly-L-lactic acid.
The present invention also protects a kind of modification Poly-L-lactic acid.
Modification Poly-L-lactic acid provided by the present invention prepares according to the method comprised the steps:
1) the multi-arm segmented copolymer shown in Poly-L-lactic acid and formula I is carried out melt blending, obtain blend;
2) by described blend injection moulding, and by the sample after plastotype 80-150 DEG C of annealing, described modification Poly-L-lactic acid is obtained.
Wherein, the number-average molecular weight of described Poly-L-lactic acid is more than 50,000.
The mass ratio of the multi-arm segmented copolymer shown in described Poly-L-lactic acid and formula I is (90-95): (5-10).
The temperature of described melt blending is 150-230 DEG C, and the blended time is 5-20min.
Described melt blending can carry out in HAAKE twin screw Banbury mixer, and wherein, before blended speed 2 ~ 5 minutes is within 10rad/min, and speed is thereafter 50 ~ 100rad/min.
Dextrorotation poly(lactic acid) block in multi-arm segmented copolymer of the present invention as physical crosslinking point, realizes the adjustment of counting out to physical crosslinking by the Stereocomplex crystal with the blended rear formation of linear Poly-L-lactic acid by the change of arm number.Soft section (polycaprolactone or PDLLA) of above-mentioned multi-arm segmented copolymer has following effect to the mechanical property improving Poly-L-lactic acid: 1) reduce Poly-L-lactic acid second-order transition temperature; 2) crystallization velocity of Poly-L-lactic acid is regulated and controled; 3) effect that island shape microcosmic disperse phase plays cushioning material internal shear power is formed.The effect that hard section in above-mentioned multi-arm segmented copolymer plays is: 1) form Stereocomplex crystalline substance with Poly-L-lactic acid and form physical crosslinking point; 2) the brilliant crystallization promoting Poly-L-lactic acid as nucleator of the Stereocomplex formed; 3) intermolecular forces of soft section of polymer dispersed phase and Poly-L-lactic acid external phase is strengthened.
The multi-arm segmented copolymer of the present invention's synthesis is mainly used in the toughness improving Poly-L-lactic acid, by the regulation and control of to the arm number of multiarm polymers and multi-arm segmented copolymer soft section (polycaprolactone or PDLLA or both multipolymers) and hard section (dextrorotation poly(lactic acid)) component, and carry out melt blending with Poly-L-lactic acid, realize the improvement to Poly-L-lactic acid mechanical property.Multi-arm segmented copolymer prepared by the present invention and Poly-L-lactic acid blended after, dispersion behavior is good, good improvement is had to the mechanical property of poly(lactic acid) under the prerequisite of basic maintenance mechanics of materials intensity, and material still has the good transparency, degradability and biocompatibility, show its important application prospect in the improvement of Poly-L-lactic acid mechanical property of multi-arm segmented copolymer.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of multi-arm segmented copolymer prepared by embodiment 1.
Fig. 2 is the nuclear-magnetism of multi-arm segmented copolymer 4a-PCL-b-PDLA prepared by embodiment 1
1h NMR spectrogram.
The Glass Transition Temperature of Fig. 3 Poly-L-lactic acid and blend thereof.
WXRD (wide-angle X ray diffractor) curve of Fig. 4 Poly-L-lactic acid and blend thereof.
DSC (differential scanning calorimeter) curve of the isothermal crystal of Fig. 5 Poly-L-lactic acid and blend thereof.
The isothermal crystal pattern of Fig. 6 Poly-L-lactic acid and blend thereof; Wherein, be respectively by a to d: (a) PLLA; (b) 4a-PCL
5k/ PLLA10/90; (c) 4a-PCL
5k-b-PLLA
5k/ PLLA 10/90; (d) 4a-PCL
5k-b-PDLA
5k/ PLLA10/90.
Fig. 7 Poly-L-lactic acid and the stress strain curve with multi-arm segmented copolymer different ratios blend thereof.
The tensile bars crossed section analysis of Fig. 8 Poly-L-lactic acid and blend thereof.Wherein be respectively by a to d: (a) PLLA; (b) 4a-PCL
5k/ PLLA 10/90; (c) 4a-PCL
5k-b-PLLA
5k/ PLLA 10/90; (d) 4a-PCL
5k-b-PDLA
5k/ PLLA10/90.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1: the synthesis of multi-arm segmented copolymer
1) synthesis of 4a-PCL-b-PDLA
Synthetic line as shown in Figure 1.First by reaction unit pump drainage 3 times; applying argon gas is protected; then the toluene solution (0.846mol/L) of 8.36g ε-own lactones, 0.2041g erythritol, 126L stannous octoate and 10mL toluene are joined in reaction tubes under argon shield, 110 DEG C of reactions two days after sealing.Then reaction tube temperature is down to room temperature, joins in reaction tubes by 8.36g dextrorotation rac-Lactide under argon shield, the oil bath of then putting into 110 DEG C continues reaction 2 ~ 3 days.Be cooled to room temperature after having reacted, by reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, finally product is put into 80 DEG C of vacuum drying ovens, vacuum-drying is to steady quality.The structure of polymerisate and composition by proton nmr spectra (
1h NMR) confirm (see Fig. 2).
2) synthesis of 4a-PDLLA-b-PDLA
Synthetic line as shown in Figure 1.First by reaction unit pump drainage 3 times; applying argon gas is protected; then the toluene solution (0.846mol/L) of 8.36g meso-lactide, 0.2041g erythritol, 126L stannous octoate and 10mL toluene are joined in reaction tubes under argon shield, 110 DEG C of reactions two days after sealing.Then reaction tube temperature is down to room temperature, joins in reaction tubes by 8.36g dextrorotation rac-Lactide under argon shield, the oil bath of then putting into 110 DEG C continues reaction 2 ~ 3 days.Be cooled to room temperature after having reacted, by reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, finally product is put into 80 DEG C of vacuum drying ovens, vacuum-drying is to steady quality.The structure of polymerisate and composition by proton nmr spectra (
1h NMR) confirm.
3)4a-P(d，1-LA-co-CL)-b-PDLA
Synthetic line as shown in Figure 1.First by reaction unit pump drainage 3 times; applying argon gas is protected; then the toluene solution (0.846mol/L) of caprolactone, meso-lactide (total mass of caprolactone and meso-lactide is 8.36g), 0.2041g erythritol, 126L stannous octoate and 10mL toluene are joined in reaction tubes under argon shield, 110 DEG C of reactions two days after sealing.Then reaction tube temperature is down to room temperature, joins in reaction tubes by 8.36g dextrorotation rac-Lactide under argon shield, the oil bath of then putting into 110 DEG C continues reaction 2 ~ 3 days.Be cooled to room temperature after having reacted, by reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, finally product is put into 80 DEG C of vacuum drying ovens, vacuum-drying is to steady quality.The structure of polymerisate and composition by proton nmr spectra (
1hNMR) confirm.
4) synthesis of other multiarm polymers
The synthesis of two arms, three arms and five arm segmented copolymers and the synthesis of above-mentioned four arm segmented copolymers similar, just change erythritol into ethylene glycol, glycerine and Xylitol respectively, reaction conditions is the same with four arm segmented copolymers with the purification processes of product.
Embodiment 2: the preparation of multi-arm segmented copolymer and Poly-L-lactic acid blend (i.e. polydactyl acid)
Four arm segmented copolymer 4a-PCL-b-PDLA prepared for embodiment 1 below and Poly-L-lactic acid is blended is described, other multi-arm segmented copolymer and the blended of Poly-L-lactic acid have same experimental conditions.
1) melt blending
Weigh Poly-L-lactic acid (PLLA) (the Natureworks company of the U.S. of 4a-PCL-b-PDLA and the 45g of 5g respectively, model is 2002D), with HAAKE twin screw Banbury mixer, multi-arm segmented copolymer and Poly-L-lactic acid are carried out melt blending, condition is as follows: blend melt temperature is 170-230 DEG C, blended speed is first 2 minutes is 10rad/min, and the speed of latter 8 minutes is 50rad/min.
2) preparation of batten
Blend batten is that the HAAKE MINI JET II of 10cc is injection molded according to ISO527-2-5A standard by capacity.By above-mentioned 1) in the sample that obtains of banburying join in injection moulding machine, wherein melt temperature is 170-230 DEG C, and the fusion time is 3min, and injection pressure is 850bar, and die temperature is 65 DEG C, and the dwell time is 10 seconds, and pressure is 100bar.
3) sample is carried out anneal
The baking oven anneal that batten injection moulding obtained puts into 80 DEG C was taken out after 4 hours, then placed at normal temperatures after at least 24 hours for further experiment.
Embodiment 3: the preparation of multi-arm segmented copolymer and Poly-L-lactic acid blend (i.e. polydactyl acid)
By embodiment 2 step 1) in the consumption of 4a-PCL-b-PDLA replace with 2.5g, the consumption of Poly-L-lactic acid (PLLA) replaces with 47.5, and other condition, all with embodiment 2, prepares polydactyl acid sample.
Embodiment 4: to the performance test of multi-arm segmented copolymer and Poly-L-lactic acid blend
A, wide-angle x-ray test (WXRD)
The batten that embodiment 2 obtains is got a part and tailor sample into 1cm × 1cm size, test with the scanning speed of 2 °/min, sweep limit is 5 ° to 40 °.Typical experimental result as shown in Figure 3, when containing dextrorotation poly(lactic acid) in segmented copolymer, at the characteristic peak of 12.0 °, 20.9 ° and 24.0 ° place's formation Stereocomplex crystalline substances in corresponding blend, illustrates containing this multi-arm segmented copolymer (4a-PCL
5k-b-PDLA
5k) blend define Stereocomplex crystalline substance, and remaining blend do not have Stereocomplex crystalline substance formed.
The isothermal crystal experiment of b, Poly-L-lactic acid and blend thereof
1) differential scanning calorimeter (DSC)
Get the blend sample of about 5mg, put into the special ware of DSC, heat-treat condition is as follows: first with the ramp to 190 of 100 DEG C/min DEG C and constant temperature 3min eliminates thermal history, be then cooled to 115 DEG C with the speed of 50 DEG C/min, and isothermal crystal 2 hours, the curve of record isothermal crystal.Experimental result as shown in Figure 4, when containing dextrorotation poly(lactic acid) in segmented copolymer, compared to other samples, the crystallization deadline of its blend obviously reduces, brilliant containing Stereocomplex in this blend as shown in Figure 3, therefore the existence of Stereocomplex crystalline substance serves the effect promoting crystallization.
2) polarisation experiment
The chloroformic solution (30mg/mL) getting 5uL blend with liquid-transfering gun drops on polarisation sheet glass, and volatilization is spent the night, and is then placed in the thermal station of 190 DEG C by this sheet glass, then tests for polarisation after getting other a slice hot pressing 3min.Thermal history is as follows: first with the ramp to 190 DEG C of 30 DEG C/min, and constant temperature 3min eliminates thermal history, is then cooled to 115 DEG C with the speed of 50 DEG C/min, and carries out isothermal crystal more than 2 hours, observes crystallization shape.Experimental result as shown in Figure 5, when containing dextrorotation poly(lactic acid) in segmented copolymer, compared to other samples, the spherocrystal density of its blend obviously increases, and spherocrystal covers with the visual field in the short period of time, brilliant containing Stereocomplex in this blend as shown in Figure 3, therefore the existence of Stereocomplex crystalline substance serves the effect of nucleator, and finally makes crystallization velocity accelerate.
C, tensile property are tested
The batten that embodiment 2 and embodiment 3 obtain at room temperature is carried out Elongation test with the rate of extension of 2mm/min, and tension load is 5kN.Puller system used is ASTM 3365, often organizes sample test more than 3.Experimental result as shown in Figure 6, when containing dextrorotation poly(lactic acid) in segmented copolymer, the elongation at break of its blend reaches about 70%, and the elongation at break of Poly-L-lactic acid homopolymer only has about 20%, illustrate that the existence of multi-arm segmented copolymer can have good lifting to the toughness of Poly-L-lactic acid.
D, batten crossed section analysis:
By batten brittle failure in liquid nitrogen, metal spraying is carried out to section, then use scanning electron microscopic observation cross-section morphology.Scanning electron microscope model used is JSM-6700F.As shown in Figure 7, compared to the transverse section of PLLA, the transverse section of the blend of segmented copolymer and PLLA obviously can form phase separation structure, and the shape of PCL disperse phase is also relatively good with distribution, thus PLLA stretch behavior is had an impact, increase the elongation at break of PLLA.
Above experimental result shows, multi-arm segmented copolymer and Poly-L-lactic acid blended after can form Stereocomplex crystalline substance, as shown in Figure 3.The Stereocomplex crystalline substance formed can play the effect promoting Poly-L-lactic acid crystallization, as shown in Figure 4 and Figure 5.Multi-arm segmented copolymer and Poly-L-lactic acid melt blending can be improved the mechanical property of Poly-L-lactic acid after anneal, be embodied under after blending little prerequisite being affected on the tensile strength of Poly-L-lactic acid material, the elongation at break of Poly-L-lactic acid can be made to significantly improve, as shown in Figure 6.By known to the analysis in material transverse section, the dispersion behavior in the blend of PCL phase is good, and the size of disperse phase is homogeneous, can play the effect of cushioning material internal shear power, as shown in Figure 7.
Claims (5)
1. the multi-arm segmented copolymer shown in formula I:
Wherein, n be more than or equal to 0 and be less than or equal to 3 integer;
for soft section, it represents the homopolymer formed by caprolactone;
for hard section, it represents dextrorotation poly(lactic acid);
In each arm of multi-arm segmented copolymer described in formula I, the number-average molecular weight of soft section is 100 ~ 100,000, and the number-average molecular weight of hard section is 700 ~ 600,000.
2. prepare the method for multi-arm segmented copolymer shown in claim 1 Chinese style I, comprise the steps:
With the polyvalent alcohol shown in formula II for initiator, under argon shield, cause 6-caprolactone monomer and carry out ring-opening polymerization, then using prepared product as macromole evocating agent, the ring-opening polymerization of further initiation dextrorotation lactide monomer, obtains described multi-arm segmented copolymer;
In formula II, n be more than or equal to 0 and be less than or equal to 3 integer;
Described polyvalent alcohol be selected from following any one:
3. method according to claim 2, is characterized in that: described ring-opening polymerization is carried out under the katalysis of catalyzer, and described catalyzer is specially stannous octoate.
4. prepare a method for modification Poly-L-lactic acid, comprise the steps:
1) the multi-arm segmented copolymer shown in Poly-L-lactic acid and formula according to claim 1 I is carried out melt blending, obtain blend;
2) by described blend injection moulding, and by the sample after plastotype 80-150 DEG C of annealing, described modification Poly-L-lactic acid is obtained;
The mass ratio of the multi-arm segmented copolymer shown in described Poly-L-lactic acid and formula I is (90-95): (5-10);
The temperature of described melt blending is 150-230 DEG C, and the blended time is 5-20min.
5. the modification Poly-L-lactic acid for preparing of method described in claim 4.
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| CN104231578B (en) * | 2014-08-29 | 2016-05-11 | 四川大学 | A kind of fully biodegradable polyester material and preparation and application thereof |
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| CN109651603A (en) * | 2019-01-23 | 2019-04-19 | 北京诺康达医药科技股份有限公司 | Controllable biodegradable copolymer material and preparation method thereof and its application |
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| CN115703923B (en) * | 2021-08-09 | 2023-09-15 | 北京化工大学 | Toughened 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 |
| CN101891881A (en) * | 2009-05-21 | 2010-11-24 | 中国科学院化学研究所 | Biodegradable high-polymer additive, preparation method and application thereof |
| CN101735582A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Poly(lactic acid)/poly(methyl methacrylate) alloy material and preparation method thereof |
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