CN103087298A - 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 the application in improving the Poly-L-lactic acid mechanical property thereof.
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 decompose under field conditions (factors) after discarded, and environment has been caused great pollution.Poly(lactic acid) does not rely on petroleum resources due to the food-based starch of monomer whose (as corn), and biodegradable, does not have the white garbage problem, and this has just greatly reduced the consumption of the energy and the pollution of environment.In recent years poly(lactic acid) particularly the replacer that is expected to as conventional plastic of Poly-L-lactic acid (PLLA) be subjected to both at home and abroad research (Anderson K et al.Toughening polylactide.Polymer Reviews 2008 widely, 48,85-108).Poly-L-lactic acid has good biocompatibility, biodegradability and the good transparency, has simultaneously very high mechanical strength (can compare favourably with polystyrene), is with a wide range of applications in fields such as daily life and biological medicines.But its second-order transition temperature higher (approximately 60 ℃), material fragility is large, and crystallization velocity is slow, thereby has extended the forming process time of goods, has reduced production efficiency.These performance deficiencies of Poly-L-lactic acid are serious must limit its widespread use in practice.Therefore, the performance that how to improve Poly-L-lactic acid realizes that also extensively utilization is the important topic that faces at present.
at present, modification conducts extensive research to Poly-L-lactic acid both at home and abroad, 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 can improve to a certain extent the performance of Poly-L-lactic acid, but because this chemical modification method needs the production technique of existing Poly-L-lactic acid is redesigned, need higher cost and time.The method that adopts physical modification is the method for simple possible comparatively.For example Poly-L-lactic acid and another degradation material polycaprolactone (PCL) are carried out blend.But the key of blend method is the selection of additive.For example, take polycaprolactone as polymeric additive, have phase separation due to after itself and Poly-L-lactic acid blend, so consistency is poor, thereby causes mechanical property effectively not 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.
The Stereocomplex crystalline substance is the characteristic of poly(lactic acid).After Poly-L-lactic acid and dextrorotation poly(lactic acid) (PDLA) are with the certain proportion blend, can form a kind of new crystal formation, be referred to as Stereocomplex crystalline substance (stereocomplex).Its fusing point is higher than 50 ℃ of left and right of fusing point (Yoshito Ikada KJ et al.Stereocomplex formation betweenenantiomeric poly (lactides) .Macromolecules 1987 of Poly-L-lactic acid, 20,904-906).Studies show that, the Stereocomplex crystalline substance has the mechanical property that is better than Poly-L-lactic acid, elongation at break and tensile modulus (H.Tsuji.Stereocomplex formation between enantiomeric poly (lactic acid) the s.XI.Mechanicalproperties and morphology of solution-cast films.Macromolecules 1999 that all increases for example, 40,6699-6708).in recent years, a kind of block copolymer structure that improves the Poly-L-lactic acid mechanical property is proposed in the world, introduce respectively soft section preferably of flexibility in this segmented copolymer, and can form with Poly-L-lactic acid the hard section of dextrorotation poly(lactic acid) (PDLA) of Stereocomplex crystalline substance, in order to 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 that improves Poly-L-lactic acid, 53, 3008-3016).Except the mechanical property of improving Poly-L-lactic acid, there are some researches show, the existence of the compound crystalline substance of polylactic acid stereoscopic under certain conditions also can be as the nucleator of Poly-L-lactic acid, thereby play the effect that promotes its crystallization, so just can reduce the crystallization time of dlactic acid, thereby 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)。
compare with linear polymer, multiarm polymers has a lot of properties, 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 (the Rahul Bhardwaj et al.Modification of brittle polylactide by novel hyperbranchedpolymer-based nanostructures.Biomacromolecules 2007 that improves to the 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 crystallization and the mechanical property of improving Poly-L-lactic acid.
Summary of the invention
The purpose 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 suc as formula shown in I:
Wherein, n is more than or equal to 0 and less than or equal to 3 integers;
Each arm forms with two blocks of hard section by soft section,
The arm number of the segmented copolymer of multi-arm shown in formula I specifically can be from 2 arms to 5 arms.
In each arm of the described multi-arm segmented copolymer of 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:
Take the polyvalent alcohol shown in formula II as initiator; under argon shield; cause 6-caprolactone monomer (CL) and/or racemization lactide monomer (d; 1-LA) carry out ring-opening polymerization; again with prepared product as macromole evocating agent; further cause the ring-opening polymerization of dextrorotation lactide monomer (d-LA), obtain described multi-arm segmented copolymer.
(formula II)
In formula II, n is more than or equal to 0 and 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 multi-arm segmented copolymer of preparation is 2 during to 5 arm, the initiator that adopts 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 arms poly-(6-caprolactone-b-dextrorotation poly(lactic acid)) (2a-PCL-b-PDLA), two arms 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:
A further 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 it in the application that improves aspect the Poly-L-lactic acid mechanical property.After this multi-arm segmented copolymer and Poly-L-lactic acid blend, the mechanical property of Poly-L-lactic acid there is good improvement, keeps mechanics of materials intensity simultaneously basic, can obviously 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 is to prepare according to the method that comprises 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) with described blend injection moulding, and with the sample after plastotype 80-150 ℃ of annealing, obtain described modification Poly-L-lactic acid.
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 ℃, and the time of blend is 5-20min.
Described melt blending can carry out in HAAKE twin screw Banbury mixer, and wherein, blend speed was in 10rad/min in front 2～5 minutes, and speed thereafter is 50～100rad/min.
Dextrorotation poly(lactic acid) block in multi-arm segmented copolymer of the present invention by with linear Poly-L-lactic acid blend after the Stereocomplex crystal that forms as the physical crosslinking point, the change by the arm number realizes adjusting that physical crosslinking is counted out.Soft section (polycaprolactone or PDLLA) of above-mentioned multi-arm segmented copolymer has following effect to the mechanical property of improving Poly-L-lactic acid: 1) reduce the Poly-L-lactic acid second-order transition temperature; 2) crystallization velocity of regulation and control Poly-L-lactic acid; 3) form the effect that island shape microcosmic disperse phase plays cushioning material internal shear power.The hard section effect of playing in above-mentioned multi-arm segmented copolymer is: 1) form the brilliant physical crosslinking point that forms of Stereocomplex with Poly-L-lactic acid; 2) the Stereocomplex crystalline substance that forms promotes the crystallization of Poly-L-lactic acid as nucleator; 3) strengthen reactive force between soft section polymer dispersed phase and Poly-L-lactic acid external phase.
The multi-arm segmented copolymer that the present invention synthesizes is mainly used in the toughness of improving Poly-L-lactic acid, by to soft section (polycaprolactone or PDLLA or both multipolymers) of the arm number of multiarm polymers and multi-arm segmented copolymer and the regulation and control of hard section (dextrorotation poly(lactic acid)) component, and carry out melt blending with Poly-L-lactic acid, realize the improvement to the Poly-L-lactic acid mechanical property.After the multi-arm segmented copolymer and Poly-L-lactic acid blend of the present invention's preparation, the dispersion behavior is good, mechanical property to poly(lactic acid) under the prerequisite of basic maintenance mechanics of materials intensity has good improvement, and material still has preferably the transparency, degradability and biocompatibility, shown the multi-arm segmented copolymer its in the Poly-L-lactic acid mechanical property important application prospect aspect improving.
Description of drawings
Fig. 1 is the synthetic route chart of the multi-arm segmented copolymer of embodiment 1 preparation.
Fig. 2 is the nuclear-magnetism of the multi-arm segmented copolymer 4a-PCL-b-PDLA of embodiment 1 preparation
1H NMR spectrogram.
The Glass Transition Temperature of Fig. 3 Poly-L-lactic acid and blend thereof.
The WXRD of Fig. 4 Poly-L-lactic acid and blend thereof (wide-angle X ray diffractor) curve.
The DSC of the isothermal crystal of Fig. 5 Poly-L-lactic acid and blend thereof (differential scanning calorimeter) curve.
The isothermal crystal pattern of Fig. 6 Poly-L-lactic acid and blend thereof; Wherein, be respectively to d by a: (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 with the stress strain curve of multi-arm segmented copolymer different ratios blend.
The tensile bars crossed section analysis of Fig. 8 Poly-L-lactic acid and blend thereof.Wherein be respectively to d by a: (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
The present invention will be described below by specific embodiment, 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: multi-arm segmented copolymer synthetic
1) 4a-PCL-b-PDLA's is synthetic
Synthetic line as shown in Figure 1.At first with reaction unit pump drainage 3 times; the applying argon gas protection; then in the toluene solution (0.846mol/L) of 8.36g ε-own lactones, 0.2041g erythritol, 126L stannous octoate and 10mL toluene being joined reaction tubes under argon shield, after sealing 110 ℃ of reactions two days.Then reaction tube temperature is down to room temperature, 8.36g dextrorotation rac-Lactide joined reaction tubes under argon shield, the oil bath of then putting into 110 ℃ continues reaction 2～3 days.Be cooled to room temperature after having reacted, reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, is put into product 80 ℃ of vacuum drying ovens at last, vacuum-drying is to steady quality.The structure and composition of polymerisate by proton nmr spectra (
1H NMR) confirm (seeing Fig. 2).
2) 4a-PDLLA-b-PDLA's is synthetic
Synthetic line as shown in Figure 1.At first with reaction unit pump drainage 3 times; the applying argon gas protection; then in the toluene solution (0.846mol/L) of 8.36g racemization rac-Lactide, 0.2041g erythritol, 126L stannous octoate and 10mL toluene being joined reaction tubes under argon shield, after sealing 110 ℃ of reactions two days.Then reaction tube temperature is down to room temperature, 8.36g dextrorotation rac-Lactide joined reaction tubes under argon shield, the oil bath of then putting into 110 ℃ continues reaction 2～3 days.Be cooled to room temperature after having reacted, reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, is put into product 80 ℃ of vacuum drying ovens at last, vacuum-drying is to steady quality.The structure and composition of polymerisate by proton nmr spectra (
1H NMR) confirm.
3)4a-P(d，1-LA-co-CL)-b-PDLA
Synthetic line as shown in Figure 1.At first with reaction unit pump drainage 3 times; the applying argon gas protection; then in the toluene solution (0.846mol/L) of caprolactone, racemization rac-Lactide (total mass of caprolactone and racemization rac-Lactide is 8.36g), 0.2041g erythritol, 126L stannous octoate and 10mL toluene being joined reaction tubes under argon shield, after sealing 110 ℃ of reactions two days.Then reaction tube temperature is down to room temperature, 8.36g dextrorotation rac-Lactide joined reaction tubes under argon shield, the oil bath of then putting into 110 ℃ continues reaction 2～3 days.Be cooled to room temperature after having reacted, reaction product by methylene chloride/methanol (v/v=1/10) dissolution/precipitation 3 times repeatedly, is put into product 80 ℃ of vacuum drying ovens at last, vacuum-drying is to steady quality.The structure and composition of polymerisate by proton nmr spectra (
1HNMR) confirm.
4) other multiarm polymers is synthetic
Synthetic and the above-mentioned four arm segmented copolymers of two arms, three arms and five arm segmented copolymers synthetic similar just changes respectively erythritol into ethylene glycol, glycerine and Xylitol and gets final product, and the purification processes of reaction conditions and product is the same with four arm segmented copolymers.
Embodiment 2: the preparation of multi-arm segmented copolymer and Poly-L-lactic acid blend (being polydactyl acid)
Below describe as an example of four arm segmented copolymer 4a-PCL-b-PDLA of embodiment 1 preparation and Poly-L-lactic acid blend example, the blend of other multi-arm segmented copolymer and Poly-L-lactic acid has same experimental conditions.
1) melt blending
The 4a-PCL-b-PDLA of difference weighing 5g and Poly-L-lactic acid (the PLLA) (U.S. Natureworks company of 45g, 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: the blend melt temperature is 170-230 ℃, the speed of blend be front 2 minutes for 10rad/min, the speed of rear 8 minutes is 50rad/min.
2) preparation of batten
The blend batten is that the HAAKE MINI JET II of 10cc is injection molded according to the ISO527-2-5A standard by capacity.With above-mentioned 1) in the sample that obtains of banburying join in injection moulding machine, wherein melt temperature is 170-230 ℃, the fusion time is 3min, injection pressure is 850bar, die temperature is 65 ℃, the dwell time is 10 seconds, pressure is 100bar.
3) sample is carried out anneal
The batten that injection moulding is obtained is put into the baking oven anneal of 80 ℃ and is taken out after 4 hours, then places at normal temperatures to be used for further experiment after at least 24 hours.
Embodiment 3: the preparation of multi-arm segmented copolymer and Poly-L-lactic acid blend (being polydactyl acid)
With embodiment 2 steps 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, other condition prepares the polydactyl acid sample all with embodiment 2.
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 is obtained is got a part and is tailored sample into 1cm * 1cm size, tests with the scanning speed of 2 °/min, and sweep limit is 5 ° to 40 °.Typical experimental result when containing the dextrorotation poly(lactic acid) in segmented copolymer, at 12.0 °, 20.9 ° and 24.0 ° of characteristic peaks of locating to form the Stereocomplex crystalline substance, illustrates and contains this multi-arm segmented copolymer (4a-PCL in corresponding blend as shown in Figure 3
5k-b-PDLA
5k) blend to have formed Stereocomplex brilliant, Stereocomplex is brilliant to be formed and remaining blend does not have.
The isothermal crystal experiment of b, Poly-L-lactic acid and blend thereof
1) differential scanning calorimeter (DSC)
Get the blend sample of 5mg left and right, put into the special-purpose ware of DSC, heat-treat condition is as follows: at first the speed with 100 ℃/min is warming up to 190 ℃ and constant temperature 3min elimination thermal history, and then the speed with 50 ℃/min is cooled to 115 ℃, and isothermal crystal 2 hours, record the curve of isothermal crystal.Experimental result as shown in Figure 4, when containing the dextrorotation poly(lactic acid) in segmented copolymer, than other samples, the crystallization deadline of its blend obviously reduces, contain the Stereocomplex crystalline substance in this blend as shown in Figure 3, so the effect that promotes crystallization has been played in the existence of Stereocomplex crystalline substance.
2) polarisation experiment
The chloroformic solution (30mg/mL) of getting the 5uL blend with liquid-transfering gun drops in polarisation with on sheet glass, and volatilization spends the night, and then this sheet glass is placed on the hot platform of 190 ℃, then is used for the polarisation experiment after getting other a slice hot pressing 3min.Thermal history is as follows: at first the speed with 30 ℃/min is warming up to 190 ℃, and constant temperature 3min elimination thermal history, and then the speed with 50 ℃/min is cooled to 115 ℃, and carries out isothermal crystal more than 2 hours, observes crystallization shape.Experimental result as shown in Figure 5, when containing the dextrorotation poly(lactic acid) in segmented copolymer, than other samples, the spherocrystal density of its blend obviously increases, and spherocrystal covers with the visual field in the short period of time, contain the Stereocomplex crystalline substance in this blend as shown in Figure 3, so the existence of Stereocomplex crystalline substance plays the effect of nucleator, and finally made crystallization velocity accelerate.
C, tensile property test
The batten that embodiment 2 and embodiment 3 are obtained at room temperature carries out Elongation test with the rate of extension of 2mm/min, and tension load is 5kN.Puller system used is ASTM 3365, and every group of sample test is more than 3.Experimental result as shown in Figure 6, when containing the dextrorotation poly(lactic acid) in segmented copolymer, the elongation at break of its blend reaches 70% left and right, and the elongation at break of Poly-L-lactic acid homopolymer only has 20% left and right, illustrates that the existence of multi-arm segmented copolymer can have to the toughness of Poly-L-lactic acid lifting preferably.
D, batten crossed section analysis:
With batten brittle failure in liquid nitrogen, section is carried out metal spraying, then use the scanning electron microscopic observation cross-section morphology.Scanning electron microscope model used is JSM-6700F.As shown in Figure 7, than the transverse section of PLLA, the transverse section of the blend of segmented copolymer and PLLA can obviously form phase separation structure, and the PCL dispersed phase is also relatively good with distribution, thereby the PLLA stretch behavior is exerted an influence, increase the elongation at break of PLLA.
Above experimental result shows, can form the Stereocomplex crystalline substance after multi-arm segmented copolymer and Poly-L-lactic acid blend, as shown in Figure 3.Formed Stereocomplex crystalline substance can play the effect that promotes the Poly-L-lactic acid crystallization, as shown in Figure 4 and Figure 5.To can improve the mechanical property of Poly-L-lactic acid after multi-arm segmented copolymer and Poly-L-lactic acid melt blending and anneal, being embodied in the tensile strength on the Poly-L-lactic acid material after blend affects under little prerequisite, the elongation at break of Poly-L-lactic acid is obviously improved, as shown in Figure 6.By to the analysis in material transverse section as can be known, the dispersion behavior of PCL in blend is good, and the big or small homogeneous of disperse phase can play the effect of cushioning material internal shear power, as shown in Figure 7.
Claims (10)
1. the multi-arm segmented copolymer shown in formula I:
Wherein, n is more than or equal to 0 and less than or equal to 3 integer;
2. multi-arm segmented copolymer according to claim 1, it is characterized in that: in each arm of the described multi-arm segmented copolymer of formula I, the number-average molecular weight of soft section is 100～100,000, the number-average molecular weight of hard section is 700～, 600,000.
3. prepare the method for multi-arm segmented copolymer shown in claim 1 Chinese style I, comprise the steps:
Take the polyvalent alcohol shown in formula II as initiator, under argon shield, cause 6-caprolactone monomer and/or racemization lactide monomer and carry out ring-opening polymerization, again with prepared product as macromole evocating agent, further cause the ring-opening polymerization of dextrorotation lactide monomer, obtain described multi-arm segmented copolymer;
In formula II, n is more than or equal to 0 and less than or equal to 3 integer.
4. method according to claim 3 is characterized in that: described polyvalent alcohol be selected from following any one:
5. according to claim 3 or 4 described methods, it is characterized in that: described ring-opening polymerization is carried out under the katalysis of catalyzer, and described catalyzer is specially stannous octoate.
6. method according to claim 5, it is characterized in that: described catalyzer is stannous octoate.
7. a method for preparing the modification Poly-L-lactic acid, comprise the steps:
1) the multi-arm segmented copolymer shown in Poly-L-lactic acid and the described formula I of claim 1 or 2 is carried out melt blending, obtain blend;
2) with described blend injection moulding, and with the sample after plastotype 80-150 ℃ of annealing, obtain described modification Poly-L-lactic acid.
8. method according to claim 7 is characterized in that: the mass ratio of the multi-arm segmented copolymer shown in described Poly-L-lactic acid and formula I is (90-95): (5-10).
9. according to claim 7 or 8 described methods, it is characterized in that: the temperature of described melt blending is 150-230 ℃, the time of blend is 5-20min.
10. the modification Poly-L-lactic acid that in claim 7-9, the described method of any one prepares.
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| CN104045984A (en) * | 2014-05-22 | 2014-09-17 | 中国科学院长春应用化学研究所 | Polylactic acid stereoscopic complex and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735582A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Poly(lactic acid)/poly(methyl methacrylate) alloy material 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 |
| 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 |
-
2013
- 2013-01-05 CN CN201310002409.2A patent/CN103087298B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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