CN102898798A - Transparent polylactic acid alloy material - Google Patents
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- CN102898798A CN102898798A CN2012102246914A CN201210224691A CN102898798A CN 102898798 A CN102898798 A CN 102898798A CN 2012102246914 A CN2012102246914 A CN 2012102246914A CN 201210224691 A CN201210224691 A CN 201210224691A CN 102898798 A CN102898798 A CN 102898798A
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Abstract
The invention discloses a transparent polylactic acid alloy material, which is prepared by polylactic acid and an elastomer by a melt mixing device through melt blending, based on the polylactic acid and the elastomer, the mass fraction of the polylactic acid accounts for 75-98% and the mass fraction of the elastomer accounts for 2-25%, and the elastomer is the elastomer containing maleic anhydride or an epoxy group. According to the invention, a certain amount of elastomer capable of being reacted with polylactic acid is added in the polylactic acid, the melt blending condition of the material is adjusted in a reasonable mode, all elastomer micro-areas are uniformly dispersed in the polylactic acid, and the disperse size is less than 100nm, thereby the transparent polylactic acid alloy material with substantially enhanced material shock resistance and fast crystallization speed of matrix polylactic acid can be obtained. A purpose that primary modification overcomes a plurality of polylactic acid application barriers can be realized. The transparent polylactic acid alloy material can be used in the industries of package, electron, building material, automobile and the like.
Description
Technical field
The present invention relates to Polymer Technology and ecological environment material nd field, relate in particular to transparent polylactic acid alloy material that a kind of impact property is high, ductility good, crystallization velocity is fast and preparation method thereof.
Background technology
Resources and environment is the great major issue of facing mankind.The tradition macromolecular material derives from non-renewable petrochemical industry resource, and before non-renewable petroleum resources dry spells arrived, macromolecular material reproducible, that particularly derive from biomass had caused global concern.In the past in 10 years, poly-lactic acid material is subject to the broad interest of industry member, and reason comprises: the one, and the poly(lactic acid) raw materials for production come from plant, do not rely on oil, before non-renewable petroleum resources dry spells arrived, reproducible product will become the well sold and in short supply product of global range.The 2nd, under certain condition can biological degradation after poly(lactic acid) is used, do not produce white pollution, this is particularly important for wrapping material.The 3rd, poly(lactic acid) belongs to a kind of less energy-consumption product, than the low 30%-50% energy consumption of the polymkeric substance take petroleum products as raw material production.The 4th, the CO2 emissions in the production of poly(lactic acid), processing and the consumption last handling process is also than general polymer material low about 20%.Therefore, the widespread use of poly-lactic acid products not only has great significance for reducing human dependence to limited resources such as oil and building low-carbon (LC) society, and can reduce white pollution, alleviates the environmental problem of facing mankind.The intensity of poly(lactic acid) own is high, but on its performance numerous deficiencies is arranged also, is mainly manifested in: 1) toughness is not enough, erosion-resisting characteristics is poor, 2) crystallization velocity is slow, shaping cycle is long, 3) second-order transition temperature is lower, uncrystallized sample poor heat resistance.This has greatly limited the widespread adoption of poly-lactic acid material.
Around the problems referred to above of poly(lactic acid) performance, existing numerous in polylactic acid modified research both at home and abroad.Aspect poly(lactic acid) impact-resistant modified: patent CN101955639A discloses a kind of method of utilizing the polyurethane elastomer plasticizing polylactic acid, and CN101168617 and CN101935390A then use aliphatic polyester to improve the shock resistance of poly(lactic acid) as toughner.JP 2007-63435 discloses a kind of method of using the polyethylene elastomer plasticizing polylactic acid.Aspect the nucleator of exploitation poly(lactic acid) rapid shaping, CN200710039825.4 uses nanometer inorganic filler as the crystallization of nucleator acceleration poly(lactic acid), shortens the shaping cycle of poly(lactic acid).The organic nucleating agent of Chinese patent application number 201110060665.8 a kind of amide containings of use prepares rapid crystallization polylactic acid.Yet all these documents all do not reach single modification can the toughness reinforcing purpose that can improve again crystallization velocity.Particularly importantly, the research of present Research on Toughening and nucleator all none other damage the properties of transparency of poly(lactic acid).How realizing accelerating the crystallization velocity of poly(lactic acid) when improving poly(lactic acid) impelling strength, do not damage the transparency of poly(lactic acid) simultaneously, is a major issue of poly-lactic acid material modification.If this research can realize, undoubtedly will greatly promote poly-lactic acid material in the application in the fields such as packaging film, engineering plastics.
Summary of the invention
The technical problem of solution required for the present invention is to utilize reactive elastomerics and poly(lactic acid) to carry out melt blending, so that elastomerics Uniform Dispersion in the poly(lactic acid) matrix, realize disperseing site diameter less than 100nm, the microcell size distribution is even, these homodisperse microcells can play again the effect of good nucleating agent in polylactic acid production simultaneously, thereby overcome the fragility of poly(lactic acid) and crystallization velocity is slow, molding time is long shortcoming, can keep again the transparency of poly(lactic acid).The invention provides a kind of based on polydactyl acid Nanoalloy material and preparation method thereof, this material and simple poly(lactic acid) ratio, shock resistance and crystallization velocity all obtain huge raising, can keep the transparency of poly-lactic acid material simultaneously.Be expected in packing, electronics, building materials, automobile and other industries, to obtain to use.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of transparent polylactic acid alloy material, described transparent polylactic acid alloy material mainly divides the melting blend to obtain by poly(lactic acid) and elastomerics through the melting mixing filling apparatus, based on described poly(lactic acid) and elastomerics, the massfraction of poly(lactic acid) is 75-98%, elastomeric massfraction is 2 ~ 25%, and described elastomerics is the elastomerics that contains maleic anhydride or epoxide group.
Here transparent polylactic acid alloy material is mainly prepared by poly(lactic acid) and elastomerics, the connotation of " mainly " is that the requisite main composition of transparent polylactic acid alloy material is these two kinds, only have these two kinds of compositions passable, but allowing also to contain some in the transparent polylactic acid alloy material does not have influential additive to major function yet yet.
The present invention can not doping, after described transparent polylactic acid alloy material is mixed by poly(lactic acid) and elastomerics, adding melting mixing equipment obtains through abundant melt blending, based on described poly(lactic acid) and elastomerics, the massfraction of poly(lactic acid) is 75-98%, elastomeric massfraction is 2 ~ 25%, and the massfraction of preferred poly(lactic acid) is 80-95%, and elastomeric massfraction is 5 ~ 20%.
Elastomerics of the present invention is the elastomerics that contains maleic anhydride or epoxide group, be in the melt blending process can with the elastomerics of poly(lactic acid) end group generation graft reaction, preferred described elastomerics is the elastomerics that contains epoxide group, preferred, described elastomerics is ethylene-acrylate-glycidyl methacrylate copolymer, the ethylene-methyl methacrylate glycidyl ester copolymer, the glycidyl methacrylate graft polyethylene, the glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethene-1-octene copolymer, glycidyl methacrylate graft ethylene-vinyl acetate copolymer or epoxide modified natural rubber, most preferably ethylene-acrylate-glycidyl methacrylate copolymer, the ethylene-methyl methacrylate glycidyl ester copolymer.In described ethylene-acrylate-glycidyl methacrylate copolymer, the acrylate in the comonomer can be one or more in methyl acrylate, ethyl propenoate, the butyl acrylate.More specifically, the AX8900 that described ethylene-acrylate-glycidyl methacrylate copolymerization can select arkema company to produce, the AX8840 that the ethylene-methyl methacrylate glycidyl ester copolymer can select arkema company to produce.Above-mentioned elastomerics all contain can with the epoxide group of poly(lactic acid) end group reaction.For realizing the nano-dispersed of elastomerics microcell, it is that oxirane value is greater than 0.01 equivalent/100g that the present invention requires the epoxy group content in the elastomerics.
Transparent polylactic acid alloy material of the present invention can also add additive, after described transparent polylactic acid alloy material is mixed by poly(lactic acid), elastomerics and additive, adding together melting mixing equipment obtains through abundant melt blending, described additive is pigment, softening agent or toughener or their arbitrary combination, the quality of described additive is the 0-40% of poly(lactic acid) and elastomeric total mass, and 0 expression wherein is infinitely close to 0 and be not 0.
In the additive of the present invention, the pigment of often selecting such as carbon black, white carbon black; The softening agent of often selecting such as polyoxyethylene glycol, dioctyl phthalate (DOP), polypropylene etc.; The toughener of often selecting such as clay, layered silicate, cage modle siloxanes.
Additive of the present invention is one of following or their arbitrary combination more preferably: layered silicate, carbon black, white carbon black, clay or cage modle siloxanes.
Melting mixing equipment of the present invention can be the various industrial melting mixing devices commonly used such as Banbury mixer, single screw extrusion machine, twin screw extruder or injector, its use-pattern as well known to those skilled in the art.When melting mixing, the smelting temperature of equipment is set in more than the melt temperature of all raw materials usually, keep the molten state of all raw materials to get final product, but smelting temperature should be lower than the thermal degradation temperature (being generally 300 ℃) of poly(lactic acid), those skilled in the art should set suitable smelting temperature according to the melting temperature of raw material.
More specifically, the temperature during melt blending of the present invention is generally 180 ~ 220 ℃.
Further, in order to obtain the nano-dispersed of elastomerics in the poly(lactic acid) matrix, need abundant melt blending during melt blending, the meaning of described abundant melt blending is, realize poly(lactic acid) and reactive elastomeric abundant reaction, this need to use higher screw speed and sufficient reaction times.In general, be twin screw extruder such as the melting mixing device, the screw speed of described twin screw extruder is generally 50 ~ 200rpm, preferred 100 ~ 200rpm; Be Banbury mixer such as the melting mixing device, the screw speed of described Banbury mixer is generally 50 ~ 200rpm, mixing time 5 ~ 20min, preferred screw speed 80 ~ 200rpm, mixing time 10 ~ 15min.
The constitutional features of the transparent polylactic acid alloy material that the present invention obtains is: elastomerics being uniformly dispersed in the poly(lactic acid) matrix, and size is less than 100 nanometers.
Transparent polylactic acid alloy material provided by the invention can by various forming technologies (such as extrusion moulding, injection molding, blow molding or calendering formation etc.) preparation alloy product, comprise film, pipe, rod, fiber yarn, plastic components etc.Goods not only can be used as wrapping material, building material, and can be used as the fields such as optical material, electronics, appliance material.By the film of the polylactic acid nano alloy material of the inventive method preparation, thickness is 200 microns and has higher transmittance (〉 65% at visible light district (400nm-700nm) when following).
Reaction principle of the present invention is, when poly(lactic acid) and elastomerics carry out melt blending in melting mixing equipment, the grafting chemical reaction can occur in poly(lactic acid) and elastomerics, thereby elastomerics can disperse with very small size (less than 100nm) in poly(lactic acid), and the bonding interface of elastomerics and poly(lactic acid) matrix is strong.
In the transparent polylactic acid alloy material provided by the invention, because elastomerics is nano-dispersed in the poly(lactic acid) matrix, this nano-elastic body microcell has the effect that improves alloy material impelling strength and ductility, still can keep the higher transparency of material simultaneously.And this nano-elastic body microcell can promote the crystallization of poly(lactic acid) matrix, thereby alloy material is except having good impelling strength, good ductility, and crystallization velocity is fast, and the forming materials cycle is short, good heat resistance.
The invention has the advantages that: 1) poly(lactic acid) content is high in the alloy material, thereby the petrochemical industry Resource Dependence degree of preparation alloy is low, is environment-friendly material.2) preparation polylactic acid alloy material shock resistance, ductility and crystallization velocity all significantly improve, and material has preferably transmittance.3) preparation only need be used melting mixing equipment commonly used, and the industry preparation is simple.
Transparent polylactic acid alloy material provided by the invention significantly improved transparent polylactic acid alloy material mechanical mechanics property, accelerated in the poly(lactic acid) process of cooling crystallization velocity, improved poly-lactic acid material forming process efficient, kept the good light transmission of poly-lactic acid material.
The present invention is by adding a certain amount of reactive elastomerics in poly(lactic acid), utilize the reaction in the melt-processed process of poly(lactic acid) and elastomerics, rationally regulate the working method of material, so that all elastomerics microcells in poly(lactic acid) be evenly distributed and size less than 100nm, thereby obtain the transparent polylactic acid alloy material that the material shock resistance significantly improves, matrix poly(lactic acid) crystallization velocity is fast.Thereby realize that a modification overcomes the target that a plurality of poly(lactic acid) are used barrier.The material of preparation is expected to use in packing, electronics, building materials, automobile and other industries.
Description of drawings
Fig. 1. the TEM figure of embodiment 1 and Comparative Examples 2 samples, wherein, Fig. 1 a is the TEM figure of Comparative Examples 2 samples, Fig. 1 b is the TEM figure of embodiment 1 sample.
Fig. 2. transmittance figure and the film sample photomacrograph of embodiment 1, Comparative Examples 1 and Comparative Examples 2 samples, wherein, Fig. 2 a is the outward appearance photo of embodiment 1 sample, and Fig. 2 b is the outward appearance photo of Comparative Examples 2 samples, Fig. 2 c is embodiment 1, the light transmittance curve figure of Comparative Examples 1 and Comparative Examples 2 film samples.
Fig. 3. the DSC temperature lowering curve figure of embodiment 1, Comparative Examples 1 ~ 3 sample.
Embodiment
In order further to understand the present invention, the present invention is described further below in conjunction with embodiment, but protection scope of the present invention is not limited in this.
Used poly-lactic acid material is that Japanese UNITIKA company produces in the embodiment of the invention, and trade names are TP4000, and its number-average molecular weight is 68000, and molecular weight distribution is 4.14,60.5 ° of C of second-order transition temperature (DSC nitrogen atmosphere 10K/min heat up mensuration).
Resulting materials tension test of the present invention is that 25 ° of C, relative humidity are to carry out in 50% the environment in temperature, uses the dumbbell shape sample, tests by ASTM D412-80 method, and tensile testing machine is Instron, and draw speed is 10mm/min.
The film shock test is tested by the standard of JIS K7160 under same envrionment conditions.
Transmittance is tested with Japanese Shimadzu ultraviolet-visible pectrophotometer, and thickness of sample is 200 microns.
The crystallization velocity of sample, is lowered the temperature with 10 ° of C/min speed after sample at first is warming up to 220 ° of C and is incubated 5 minutes with the differential scanning calorimetry instrument test of U.S. TA company.
Embodiment 1
Used elastomerics is ethylene-acrylate-glycidyl methacrylate copolymer, and the weight fraction of ethene, acrylate, glycidyl methacrylate is 68%, 22% and 10%, and oxirane value is 0.07 equivalent/100g, and melting index is 6g/10min.Sample is available from French arkema company, and trade names are AX8900.With poly(lactic acid) (PLA) and elastomerics respectively in 80 ℃ of vacuum drying ovens after dry 24 hours, be the ratio in 80:20 according to PLA, elastomeric mass ratio, add in the Banbury mixer behind the mix and blend under the room temperature, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, and mixing time is 15min.
The hot pressing in 210 ℃ thermocompressor of above-mentioned mixing sample is in blocks, carry out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
Embodiment 2
Elastomerics is the ethylene-methyl methacrylate glycidyl ester copolymer, and the massfraction of ethene, glycidyl methacrylate is 92% and 8%, and oxirane value is 0.056 equivalent/100g.Melting index is 5g/min.Sample is available from French arkema company, and trade names are AX8840.With poly(lactic acid) (PLA) and elastomerics respectively in 80 ℃ of vacuum drying ovens after dry 24 hours, be the ratio in 80:20 according to PLA, elastomeric mass ratio, add in the Banbury mixer behind the mix and blend under the room temperature, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, and mixing time is 15min.
The hot pressing in 210 ℃ thermocompressor of above-mentioned mixing sample is in blocks, carry out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
Embodiment 3-embodiment 5
Elastomerics is with embodiment 1, and other operate with embodiment 1, and difference is, wherein poly(lactic acid) and elastomerics mass ratio are respectively 85:15,90:10,95:5, prepare mixing sample by embodiment 1 same working method, and test result is as shown in table 1.
Comparative Examples 1
Poly(lactic acid) is added in the Banbury mixer, and the Banbury mixer temperature is 200 ℃, and the setting screw speed is 100rpm, banburying discharging after 5 minutes.
Sheet with above-mentioned mixing sample is hot pressed in 210 ℃ thermocompressor carries out performance test with standard dumbbell shape punching press cutter preparation standard test batten, and the result is as shown in table 1.
Comparative Examples 2
Various operations and condition are with embodiment 1, and difference is that the sample mixing time is 5 minutes.
The hot pressing in 210 ℃ thermocompressor of above-mentioned mixing sample is in blocks, carry out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
Comparative Examples 3
Poly(lactic acid) and talcum powder are added in the Banbury mixer, and the Banbury mixer temperature is 200 ℃, and the setting screw speed is 100rpm, banburying discharging after 5 minutes.
The hot pressing in 210 ℃ thermocompressor of above-mentioned mixing sample is in blocks, carry out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
As can be seen from Table 1, the used elastomerics that contains epoxy has significantly improved shock resistance and the elongation at break of poly(lactic acid) gold copper-base alloy.Simultaneously under the prerequisite that epoxide group fully reacts, the transmittance of the material of institute shows that all greater than 80% preparing material has the good transparency.In addition, the crystallization velocity of all transparent alloy materials significantly improves, even is higher than talc poly(lactic acid) system commonly used.
Table 1: the performance of transparent polylactic acid alloy material
The microtexture (TEM) of embodiment 1 and Comparative Examples 2 samples as shown in Figure 1.Wherein, Fig. 1 a is the TEM figure of Comparative Examples 2 samples, and Fig. 1 b is the TEM figure of embodiment 1 sample.As can be seen from the figure, the size of all microcells is all less than 100nm among the embodiment 1, and site size is evenly distributed, and obtains the Nanoalloy of poly(lactic acid).Therewith contrast, although the sample prescription of Comparative Examples 2 is identical with embodiment 1, site size is about 1 micron.Comparative Examples 2 is mixing time with the difference of embodiment 1, this shows, needs the sufficient reaction times to realize poly(lactic acid) and reactive elastomeric abundant reaction, to obtain the nano-dispersed of elastomerics in the poly(lactic acid) matrix.
Macroscopical picture of embodiment 1 and Comparative Examples 2 film samples is shown in Fig. 2 a and Fig. 2 b.Wherein, Fig. 2 a is the outward appearance picture of embodiment 1 sample, and Fig. 2 b is the outward appearance picture of Comparative Examples 2 samples, and thickness is 200 microns.Although embodiment 1 is identical with the prescription of Comparative Examples 2 samples, the sample that embodiment 1 obtains is the Nanoalloy of poly(lactic acid), and is transparent, transmittance is high, and the film sample of Comparative Examples 2 is that oyster white, transmittance are low.This be since Nanoalloy in the nanometer site size be significantly smaller than visible light wavelength, to visible scattering of light, the reflection little, thereby sample is transparent.
Fig. 2 c is embodiment 1, the light transmittance curve figure of Comparative Examples 1 and Comparative Examples 2 film samples, and thickness is 200 microns.Can obviously find out among the figure, embodiment 1 is very approaching with the transmittance of the pure poly-lactic acid material of Comparative Examples 1, and the transmittance of Comparative Examples 2 samples is significantly lower.
Embodiment 1 and Comparative Examples 1-3 sample are from the DSC curve of 10 ℃/min of high temperature cooling as shown in Figure 3.Obvious pure poly(lactic acid) (Comparative Examples 1) and the matrix material with large size microcell do not have the peak crystallization of heat release in temperature-fall period, illustrate that these two sample crystallization velocitys are slow.And the sample of embodiment 1 has an obvious peak crystallization, the peak position of peak crystallization is 116 ℃, compare with having added the talcous Comparative Examples 3 that is commonly used to as nucleating agent in polylactic acid production, the Tc peak value is higher, illustrates that the nucleating effect of nanometer microcell is higher than talcum powder.
Claims (10)
1. transparent polylactic acid alloy material, it is characterized in that described transparent polylactic acid alloy material mainly divides the melting blend to obtain by poly(lactic acid) and elastomerics through the melting mixing filling apparatus, based on described poly(lactic acid) and elastomerics, the massfraction of poly(lactic acid) is 75-98%, elastomeric massfraction is 2 ~ 25%, and described elastomerics is the elastomerics that contains maleic anhydride or epoxide group.
2. transparent polylactic acid alloy material as claimed in claim 1 is characterized in that described elastomerics is the elastomerics that contains epoxide group.
3. transparent polylactic acid alloy material as claimed in claim 1 is characterized in that described elastomerics is ethylene-acrylate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethene-1-octene copolymer, glycidyl methacrylate graft ethylene-vinyl acetate copolymer or epoxide modified natural rubber.
4. elastomerics as claimed in claim 3, its constitutional features is that described elastomeric oxirane value is greater than 0.01 equivalent/100g.
5. transparent polylactic acid alloy material as claimed in claim 1, it is characterized in that described transparent polylactic acid alloy material is mixed by poly(lactic acid) and elastomerics after, add melting mixing equipment and obtain through abundant melt blending.
6. transparent polylactic acid alloy material as claimed in claim 5, after it is characterized in that described transparent polylactic acid alloy material is mixed by poly(lactic acid) and elastomerics, adding melting mixing equipment obtains through abundant melt blending, based on described poly(lactic acid) and elastomerics, the massfraction of poly(lactic acid) is 80-95%, and elastomeric massfraction is 5 ~ 20%.
7. transparent polylactic acid alloy material as claimed in claim 1, after it is characterized in that described transparent polylactic acid alloy material is mixed by poly(lactic acid), elastomerics and additive, adding melting mixing equipment obtains through abundant melt blending, described additive is pigment, softening agent or toughener or their arbitrary combination, and the quality of described additive is the 0-40% of poly(lactic acid) and elastomeric total mass.
8. such as the described transparent polylactic acid alloy material of one of claim 5 ~ 7, it is characterized in that described melting mixing equipment is twin screw extruder, the screw speed of described twin screw extruder is 100 ~ 200rpm.
9. such as the described transparent polylactic acid alloy material of one of claim 5 ~ 7, it is characterized in that described melting mixing equipment is Banbury mixer, the screw speed of described Banbury mixer is 80 ~ 200rpm, mixing time 10 ~ 20min.
10. the application for preparing alloy product film, pipe, rod, fiber yarn or plastic components by moulding process such as the described polylactic acid alloy material of one of claim 1 ~ 7.
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| CN104530666A (en) * | 2014-12-08 | 2015-04-22 | 安徽聚美生物科技有限公司 | High-temperature-resistant polylactic acid degradable material, high-temperature-resistant polylactic acid injection molded tableware, and preparation methods thereof |
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| CN105440608A (en) * | 2015-04-16 | 2016-03-30 | 湖南工业大学 | High-toughness high-strength polylactic acid composite material and preparation process therefor |
| CN105713361A (en) * | 2016-04-05 | 2016-06-29 | 大连理工大学 | Toughening impact-resistant polylactic acid based on epoxidized TPE (thermoplastic elastomer) and preparation method of toughening impact-resistant polylactic acid |
| CN105778447A (en) * | 2016-03-11 | 2016-07-20 | 大连理工大学 | Shock resistant polylactic acid and preparation method thereof |
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| CN108440926A (en) * | 2018-03-26 | 2018-08-24 | 四川大学 | High-performance Stereocomplex type polylactic acid/elastomer alloy material or product and preparation method thereof |
| CN111978696A (en) * | 2020-08-17 | 2020-11-24 | 咖法科技(上海)有限公司 | Tea leaf residue polylactic acid and preparation method thereof |
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| CN113943406A (en) * | 2021-05-08 | 2022-01-18 | 天津科技大学 | Preparation method of intelligent temperature-control reversible light-transmitting material |
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| CN105440608A (en) * | 2015-04-16 | 2016-03-30 | 湖南工业大学 | High-toughness high-strength polylactic acid composite material and preparation process therefor |
| CN105440608B (en) * | 2015-04-16 | 2017-04-19 | 湖南工业大学 | High-toughness high-strength polylactic acid composite material and preparation process therefor |
| CN105778447A (en) * | 2016-03-11 | 2016-07-20 | 大连理工大学 | Shock resistant polylactic acid and preparation method thereof |
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| CN111978696A (en) * | 2020-08-17 | 2020-11-24 | 咖法科技(上海)有限公司 | Tea leaf residue polylactic acid and preparation method thereof |
| CN113943406A (en) * | 2021-05-08 | 2022-01-18 | 天津科技大学 | Preparation method of intelligent temperature-control reversible light-transmitting material |
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