CN109836790A - High-performance stereocomplex PLA material with superior low temperature mobility and preparation method thereof - Google Patents
High-performance stereocomplex PLA material with superior low temperature mobility and preparation method thereof Download PDFInfo
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- CN109836790A CN109836790A CN201910134444.7A CN201910134444A CN109836790A CN 109836790 A CN109836790 A CN 109836790A CN 201910134444 A CN201910134444 A CN 201910134444A CN 109836790 A CN109836790 A CN 109836790A
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Abstract
A kind of high-performance stereocomplex PLA material and preparation method thereof with superior low temperature mobility disclosed by the invention, the material is after being premixed high-melting-point Stereocomplex type polylactic acid and low melting point Stereocomplex type polylactic acid at room temperature, it is formed again through melt blending, is 3.8 × 10 in 220 DEG C of the at a temperature of shear viscosity that measures2~1.8 × 103Pa.s, and its 220 DEG C at a temperature of through injection molding obtain SC-PLA product crystallinity be 45.8~57.3%, Vicat softening point be 192.2~227.3 DEG C, breaking strength be 60.9~72.5MPa.Material disclosed by the invention both can not higher than 220 DEG C at a temperature of squeeze out or injection molding, ensure that the SC-PLA product material mechanical property with higher and heat resistance of acquisition, and simple process efficiently, be easily industrialized production.
Description
Technical field
The invention belongs to stereocomplex PLA and its preparation technical fields, and in particular to one kind has superior low temperature flowing
The high-performance stereocomplex PLA material and preparation method thereof of property.
Background technique
Polylactic acid (PLA) be most widely used at present and most promising biology base degradable high polymer material it
One.Since PLA has the characteristics that biocompatibility, biodegradability, the higher transparency and excellent mechanical strength, because
This is applied to the fields such as bio-medical material and packaging material in large quantities.However, although its mechanical strength and nylon, poly- carbon
The engineering plastics such as acid esters and polyformaldehyde are suitable, but since the crystalline rate of PLA is very slow, using the side of general injection molding
Product crystallinity made from method be it is very low, heat resistance is also excessively poor, and heat distortion temperature only has 60 DEG C or so, this is just greatly limited
It has been made in the application of engineering field.In recent years, the appearance of Stereocomplex type polylactic acid (SC-PLA) is the engineering of PLA material
Using providing new thinking.
SC-PLA is a kind of PLA obtained from being blended as the l-lactic acid (PLLA) of equivalent with dextrorotation polylactic acid (PDLA)
Material.In SC-PLA, the strand of PLLA and PDLA are mutually paired in the form of in harness and under intermolecular hydrogen bonding effects
Closely pile up to form Stereocomplex (SC) crystal.The fusing point of this SC crystal is about 230 DEG C, is respectively crystallized than PLLA or PDLA
The fusing point of homogeneous (HC) crystal of formation is higher by 50 DEG C.The formation of a large amount of SC crystal can significantly improve the heat resistance of PLA, simultaneously
SC crystal can also effectively improve the performances such as mechanical property, thermal stability, hydrolytic resistance and the durability of PLA.
The formation of SC crystal is closely related with the size of PLA weight average molecular weight.When PLLA or PDLA weight average molecular weight compared with
(it is less than or equal to 1 × 10 when low4g.mol-1), it is easy to form the SC crystal of high-content during fusion-crystallization.But work as PLLA
Or PDLA weight average molecular weight it is higher when (be greater than 1 × 104g.mol-1), in SC-PLA while forming SC crystal often
With the generation of a large amount of HC crystal, the excellent properties for eventually leading to SC crystal, which are unable to get, to be given full play to.And in actual application
In the middle, only when the preferable product of mechanical property is prepared in the higher Shi Caineng of the weight average molecular weight of PLA.Therefore, in order to prepare
The SC-PLA product for having both high-fire resistance, excellent mechanical intensity just must try to improve in high molecular weight SC-PLA product
The crystallinity and relative amount of SC crystal can just be met the requirements.Otherwise, can only just look for another way to meet the requirements.Such as CN
103965493 A just use the technology of the micro- crosslinking of solid-state during melt blending prepares high molecular weight SC-PLA material,
The micro- crosslinking of selectivity is carried out with PDLA strand with the amorphous area PLLA to SC-PLA, is formed by the structure of this micro- crosslinking just
PLLA and PDLA strand can be connected by chemical bond, to guarantee SC-PLA material re-melting processing system
During standby SC-PLA product, PLLA the and PDLA strand matched in SC crystal is not destroyed, and is re-formed while cooling
The SC crystal of a large amount of high-purity and high-content, and then effectively improve the heat resistance of SC-PLA product.But by SC-PLA material
During expecting melt-processed, the mobility of SC-PLA when to guarantee melt molding, processing temperature will be in SC crystalline melting point (~230
DEG C) more than (general be not less than 240 DEG C), will lead to the serious reduction of SC-PLA Mechanical Properties of Products etc. again at high temperature.This is
Because ester bond is easily broken off and leads to PLA molecular weight at high temperature containing a large amount of thermally sensitive ester bonds in PLA molecular backbone
It reduces.
Therefore, in order to which SC-PLA product with high performance is prepared in the method by melt molding, it is necessary to will be at
Type temperature control be not higher than 220 DEG C, by SC-PLA material lower than SC crystalline melting point at a temperature of carry out it is so-called " low temperature at
Type ".104788921 A of CN be exactly by lower than SC crystalline melting point at a temperature of to dystectic SC-PLA material into
Row sinter molding is prepared for SC-PLA product with high performance.In this process first in the temperature for being lower than SC crystalline melting point
Degree is lower to apply high pressure, is closely contacted with each other SC-PLA powder particle, then by its low-temperature sintering, adjacent during the sintering process
PLLA and PDLA strand in granular boundary phase counterdiffusion One-step crystallization of going forward side by side forms new SC crystal in grain, finally obtains
Product.Although this forming method can be avoided that again PLA strand is serious at high temperature while preventing SC crystal split-phase
Degradation, but since the mobility of SC-PLA powder is very poor, can not be squeezed out or be infused using common device of plastic processing
It is moulded into type, can only be by the compression moulding at a higher pressure of customized press device, therefore not only equipment cost is very high,
And the method for compression moulding is difficult to that complex-shaped product is prepared；High pressure compression moulding energy consumption is higher simultaneously, and the time is longer,
The cost of product molding is increased, undoubtedly will affect the popularization of the technique.Therefore in order to realize high-performance SC-PLA product work
The large-scale production and application of industry, it is necessary to improve SC-PLA material not higher than 220 DEG C at a temperature of mobile performance (i.e.
Improve its low temperature fluidity), in favor of efficient extrusion or injection molding.
Summary of the invention
The object of the present invention is to provide a kind of high-performance stereocomplex PLA material with superior low temperature mobility.
It is a kind of with superior low temperature mobility it is another object of the present invention in view of the problems of the existing technology, provide
The preparation method of high-performance stereocomplex PLA material.
A kind of high-performance stereocomplex PLA material with superior low temperature mobility provided by the invention, feature exist
It is to be formed by formula as below through melt blending by weight in the material:
20~90 parts of high-melting-point Stereocomplex type polylactic acid (SC-hPLA)
10~80 parts of low melting point Stereocomplex type polylactic acid (SC-lPLA),
It is 3.8 × 10 in 220 DEG C of the at a temperature of shear viscosity that measures2~1.8 × 103Pa.s, and it is at 220 DEG C
At a temperature of through injection molding obtain SC-PLA product crystallinity be 45.8~57.3%, Vicat softening point be 192.2~
227.3 DEG C, breaking strength is 60.9~72.5MPa.
The fusing point of high-melting-point Stereocomplex type polylactic acid described in the above material is 227~244 DEG C, and the low melting point founds structure
The fusing point of compound polylactic acid is 185~213 DEG C.
SC-lPLA component can be used as mobile phase under the melt processing temperature not higher than 220 DEG C and effectively mention in the above material
The low temperature fluidity of high SC-hPLA is conducive to the extrusion or injection molding of SC-PLA material；Furthermore adding not higher than 220 DEG C
Work temperature can effectively inhibit the serious degradation of PLA strand, and the SC-hPLA component work in-process not melted in material can
SC crystal is formed efficiently to induce SC-lPLA component to crystallize, therefore guarantees obtained SC-PLA product mechanical property with higher
Energy and heat resistance.
When the above material is preferably formed by formula as below through melt blending by weight:
30~90 parts of high-melting-point Stereocomplex type polylactic acid (SC-hPLA)
10~70 parts of low melting point Stereocomplex type polylactic acid (SC-lPLA),
It is 5.1 × 10 in 220 DEG C of the at a temperature of shear viscosity that measures2~1.8 × 103Pa.s, and it is at 220 DEG C
At a temperature of through injection molding obtain SC-PLA product crystallinity be 47.4~57.3%, Vicat softening point be 197.6~
227.3 DEG C, breaking strength is 67.6~72.5MPa.
The preparation side of the above-mentioned high-performance stereocomplex PLA material with superior low temperature mobility provided by the invention
Method, it is characterised in that the processing step and condition of this method are as follows:
1) by 20~90 parts of high-melting-point Stereocomplex type polylactic acid (SC-hPLA), low melting point Stereocomplex type polylactic acid
(SC-lPLA) it is premixed at room temperature for 10~80 parts；
2) gained premix is added in melt mixer, 160~220 DEG C at a temperature of at least mix 10 minutes, i.e.,
The high-performance SC-PLA material with superior low temperature mobility can be obtained,
The number of above each material is parts by weight.
The fusing point of high-melting-point Stereocomplex type polylactic acid used in above method is 227~244 DEG C, low melting point used
The fusing point of Stereocomplex type polylactic acid is 185~213 DEG C.
SC-hPLA used in above method or SC-lPLA can be total by the melting disclosed in 102532837 A of CN
It is prepared by mixed object method, and SC-hPLA be by optical purity >=97.6% l-lactic acid (PLLA) and optical purity >=
97.6% dextrorotation polylactic acid (PDLA) is blended and obtains；SC-lPLA is the PLLA and light for being 90.7~96.0% by optical purity
The PDLA that purity is 90.7~96.0% is learned to be blended and obtain；The weight average molecular weight of PLLA or PDLA used are 5.0 × 104~
1.5×106g.mol-1；The weight ratio of PLLA and PDLA is 1:1 in SC-hPLA and SC-lPLA.
High-melting-point Stereocomplex type polylactic acid used in above method is preferably 30~90 parts, and low melting point used founds structure
Compound polylactic acid is preferably 10~70 parts.
Above method resulting materials carry out extrusion or injection molding, Ke Yibao under 215~220 DEG C of melt processing temperature
Demonstrate,prove the mechanical property and heat resistance with higher of resulting product.
Compared with prior art, the present invention having the advantage that
1. since the SC-lPLA component contained in high-performance stereocomplex PLA material provided by the invention can be not high
It is used as mobile phase under 220 DEG C of melt processing temperature, the low temperature fluidity of SC-hPLA powder is effectively improved, so that SC-
PLA material can not higher than 220 DEG C at a temperature of squeeze out or injection molding, thus on the one hand overcome existing high pressure pressure
Forming method processed the shortcomings that time-consuming, inefficiency, conventional high-temperature (>=240 DEG C) injection molding forming method is on the other hand overcome again
It is middle seriously degrade because of PLA strand caused by SC-PLA product properties the shortcomings that seriously reducing, be conducive to that high-performance is prepared
SC-PLA product.
2. being not higher than 220 DEG C of melting due to also containing in high-performance stereocomplex PLA material provided by the invention
The SC-hPLA component not melted under processing temperature, and this constituent part mechanical property with higher itself, and processed
SC-lPLA component can be efficiently induced to crystallize to form SC crystal in journey, hereby it is ensured that the SC-PLA material obtained is with higher
Mechanical property and heat resistance.
3. due to the present invention is to provide a kind of high-performance SC-PLA material with superior low temperature mobility, thus not only
It can be processed by common extrusion or injection-moulding device, save existing high pressure briquetting process bring equipment investment,
Production cost is reduced, and simple process is efficient, is easily industrialized production.
Detailed description of the invention
Fig. 1 be the obtained SC-PLA material of the embodiment of the present invention 1 and comparative example 1 when 220 DEG C viscosity with shear rate
Change curve.SC-PLA material does not almost melt in comparative example 1 as seen from the figure, therefore material internal and material and metal
The frictional force of equipment room is very big, causes the viscosity of system high.And embodiment 1 has fusing point because being added in SC-hPLA component
The SC-lPLA component of lower (185 DEG C), the component can melt completely at 220 DEG C in addition, and effectively reduce as mobile phase
The flow resistance of SC-hPLA, therefore the viscosity of the system has dropped two orders of magnitude.
Fig. 2 is for SC-PLA material obtained in the embodiment of the present invention 1 and comparative example 1 with the micro injection molding machine of HAAKE in 220 DEG C
At a temperature of mold filling digital pictures.The viscosity of SC-PLA material as used in comparative example 1 is too high, and mobility is too poor, Cong Tuzhong
It can be seen that its can not mold filling form complete sample；And SC-PLA material used in the embodiment of the present invention 1 has lower glue
Degree, mobile performance is preferable, therefore can completely mold filling form complete sample.
Fig. 3 is that the embodiment of the present invention 1~5 is micro with HAAKE at 220 DEG C with SC-PLA material in comparative example 2~3
X-ray diffraction (XRD) curve graph for the SC-PLA product that injection molding machine is molded.It can be seen from the figure that Examples 1 to 5 institute
The characteristic peak for having obviously SC crystal on the XRD curve of SC-PLA product is obtained, shows to form a large amount of SC crystalline substance in product
Body, and its crystallinity is between 45.8-57.3%；Although there is the characteristic peak of SC crystal on the XRD curve of comparative example 2 and 3,
It is that peak intensity significantly reduces, the crystallinity of SC crystal only has 16.7% and 18.6% respectively.
Specific embodiment
Embodiment is given below so that the present invention to be specifically described, but it is necessarily pointed out that following embodiment
It is only used for that invention is further explained, should not be understood as limiting the scope of the invention, the technology in the field is ripe
Practice personnel's some nonessential modifications and adaptations that content makes the present invention according to the present invention and still belongs to protection scope of the present invention.
It is worth noting that the number of material used in following embodiment and comparative example is parts by weight.
Embodiment 1
First by 20 parts of fusing points be 227 DEG C SC-hPLA, 80 parts of fusing points be 185 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 160 DEG C at a temperature of mix 10 minutes, can be obtained with excellent
The high-performance SC-PLA intermingling material of different low temperature flow.Wherein SC-hPLA used be respectively 97.6% He by optical purity
97.6%, weight average molecular weight is respectively 5 × 104g.mol-1With 5 × 104g.mol-1PLLA and PDLA is blended obtains；It is used
SC-lPLA be respectively 90.7% and 90.7% by optical purity, weight average molecular weight is respectively 5 × 104g.mol-1With 5 ×
104g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Embodiment 2
First by 40 parts of fusing points be 237 DEG C SC-hPLA, 60 parts of fusing points be 196 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 180 DEG C at a temperature of mix 10 minutes, can be obtained with excellent
The high-performance SC-PLA intermingling material of different low temperature flow.Wherein SC-hPLA used be respectively 99.0% He by optical purity
99.0%, weight average molecular weight is respectively 2.5 × 105 g.mol-1With 2.7 × 105g.mol-1PLLA and PDLA is blended obtains；
SC-lPLA used be respectively 93.1% and 93.1% by optical purity, weight average molecular weight is respectively 1.5 × 105g.mol-1With
1.8×104 g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Embodiment 3
First by 90 parts of fusing points be 244 DEG C SC-hPLA, 10 parts of fusing points be 213 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 220 DEG C at a temperature of mix 10 minutes, can be obtained with excellent
The high-performance SC-PLA intermingling material of different low temperature flow.Wherein SC-hPLA used be respectively 99.9% He by optical purity
99.9%, weight average molecular weight is respectively 1.5 × 106 g.mol-1With 1.5 × 106g.mol-1PLLA and PDLA is blended obtains；
SC-lPLA used be respectively 96.0% and 96.0% by optical purity, weight average molecular weight is respectively 1.5 × 106g.mol-1With
1.5× 106g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Embodiment 4
First by 60 parts of fusing points be 241 DEG C SC-hPLA, 40 parts of fusing points be 199 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 210 DEG C at a temperature of mix 10 minutes, can be obtained with excellent
The high-performance SC-PLA intermingling material of different low temperature flow.Wherein SC-hPLA used be respectively 99.2% He by optical purity
99.2%, weight average molecular weight is respectively 5.0 × 105 g.mol-1With 5.5 × 105g.mol-1PLLA and PDLA is blended obtains；
SC-lPLA used be respectively 93.7% and 93.7% by optical purity, weight average molecular weight is respectively 6.2 × 105g.mol-1With
4.5×105 g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Embodiment 5
First by 30 parts of fusing points be 231 DEG C SC-hPLA, 70 parts of fusing points be 190 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 170 DEG C at a temperature of mix 10 minutes, can be obtained with excellent
The high-performance SC-PLA intermingling material of different low temperature flow.Wherein SC-hPLA used be respectively 98.0% He by optical purity
98.0%, weight average molecular weight is respectively 1.5 × 105 g.mol-1With 1.8 × 105g.mol-1PLLA and PDLA is blended obtains；
SC-lPLA used be respectively 92.2% and 92.2% by optical purity, weight average molecular weight is respectively 2.1 × 105g.mol-1With
1.9×105 g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Comparative example 1
By 100 parts of fusing points be 227 DEG C SC-hPLA be added torque rheometer in 160 DEG C at a temperature of mixing 10 minutes,
Obtain SC-PLA material.SC-hPLA used in it be respectively 97.6% and 97.6% by optical purity, weight average molecular weight point
It Wei 5 × 104g.mol-1With 5 × 104g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Comparative example 2
By 100 parts of fusing points be 185 DEG C SC-lPLA be added torque rheometer in 160 DEG C at a temperature of mixing 10 minutes,
Obtain SC-PLA material.SC-lPLA used in it be respectively 90.7% and 90.7% by optical purity, weight average molecular weight point
It Wei 5 × 104g.mol-1With 5 × 104g.mol-1PLLA and PDLA be blended to obtain with the weight ratio of 1:1.
Comparative example 3
First by 20 parts of fusing points be 227 DEG C SC-hPLA, 80 parts of fusing points be 185 DEG C SC-lPLA be mixed in advance at room temperature
It is even, then by gained premix be added torque rheometer in 160 DEG C at a temperature of mix 10 minutes, SC-PLA can be obtained
Intermingling material.Wherein SC-hPLA used be respectively 97.6% and 97.6% by optical purity, weight average molecular weight is respectively 5 ×
104g.mol-1With 5 × 104g.mol-1PLLA and PDLA is blended obtains；SC-lPLA used is to be respectively by optical purity
90.7% and 90.7%, weight average molecular weight is respectively 5 × 104g.mol-1With 5 × 104g.mol-1PLLA and PDLA with 1:1's
Weight ratio is blended to obtain.
In order to investigate the correlated performance of resulting materials of the present invention, the present invention to the obtained material of embodiment and comparative example,
Mobile performance, crystal property, heat resistance and tensile property test are carried out.Wherein the mobile performance of material be by embodiment and
SC-PLA material obtained by comparative example directly measures, and in order to characterize material crystalline performance, heat resistance and tensile property, then it is first
First by SC-PLA material 220 DEG C at a temperature of carry out injection molding with the micro injection molding machine of HAAKE and obtain SC-PLA product, so
Acquisition is tested for the property to obtained product afterwards.
1) the mobile performance test of material: the shear viscosity of embodiment and comparative example resulting materials is by Rosand RH7/10
As a result the measurement that type (Malvern company, Britain) high pressure capillary rheometer carries out, shear rate 100Hz are seen attached list；
2) injection molding system the crystal property test of material: is characterized with the result of X ' Pert Pro MPD type X-ray diffractometer
The crystalline state of product, X-ray are under the electric field of 40kV voltage and 40mA electric current by thermoelectron excitation Cu target and by Ni filter disc mistake
Obtained K alpha ray, wavelength 0.154nm are filtered, pattern diffraction angular region is 5-40 °, and scanning speed is 5 °/min, will be thus bent
The crystallinity that line computation obtains is listed in subordinate list；
3) the heat resistance test of material: injection-molded item is subjected to Vicat softening point test, to characterize its heat resistance
Just.Specifically measured using XWB-300A type (irrigating auspicious intelligent technology limited in Suzhou pavilion) thermal deformation vicat softening point temperature
Instrument measures its Vicat softening point, selects ISO306 standard, and heating rate is 120 DEG C/h, load 10N.Test result is seen attached list；
4) the tensile property test of material: injection-molded item (is newly thought carefully limited in Shenzhen using the omnipotent mechanics machine of SANS
Company) the stretching experiment test that carries out, rate of extension 5mm/min, test result sees attached list.
Subordinate list
* listed shear viscosity is that speed is sheared in " shear rate-shear viscosity " curve measured by high pressure capillary in table
The shear viscosity of rate corresponding material when being 100Hz.
By the test result of subordinate list as it can be seen that the SC-lPLA being added in the present invention 220 DEG C at a temperature of can make SC-
The viscosity of hPLA is in the reduction of the order of magnitude, the low temperature fluidity of SC-hPLA is effectively improved, so that SC-PLA material can
It is formed in the method by traditional extrusion or injection molding.Further, since low temperature process can effectively inhibit PLA strand
Degradation, the SC-PLA product mechanical property with higher because obtained from；And since the SC-hPLA component not melted is being processed
In the SC-PLA product heat resistance with higher that can efficiently induce SC-lPLA component to crystallize to form SC crystal, therefore obtain
Energy.
Claims (5)
1. a kind of high-performance stereocomplex PLA material with superior low temperature mobility, it is characterised in that the material is by weight
Part meter is to be formed by formula as below through melt blending:
20~90 parts of polylactic acid of high-melting-point Stereocomplex type
10~80 parts of polylactic acid of low melting point Stereocomplex type,
It is 3.8 × 10 in 220 DEG C of the at a temperature of shear viscosity that measures2~1.8 × 103Pa.s, and it is in 220 DEG C of temperature
The lower crystallinity for obtaining SC-PLA product through injection molding is 45.8~57.3%, and Vicat softening point is 192.2~227.3 DEG C,
Breaking strength is 60.9~72.5MPa.
2. the high-performance stereocomplex PLA material according to claim 1 with superior low temperature mobility, feature
The fusing point for being high-melting-point Stereocomplex type polylactic acid described in the material is 227~244 DEG C, and it is multiple that the low melting point founds structure
The fusing point of mould assembly polylactic acid is 185~213 DEG C.
3. a kind of preparation side of the high-performance stereocomplex PLA material described in claim 1 with superior low temperature mobility
Method, it is characterised in that the processing step and condition of this method are as follows:
1) at room temperature by 20~90 parts of high-melting-point Stereocomplex type polylactic acid, 10~80 parts of low melting point Stereocomplex type polylactic acid
It is premixed；
2) by gained premix be added melt mixer in, 160~220 DEG C at a temperature of at least mix 10 minutes, can obtain
To the high-performance SC-PLA material with superior low temperature mobility,
The number of above each material is parts by weight.
4. the preparation side of the high-performance stereocomplex PLA material according to claim 3 with superior low temperature mobility
Method, it is characterised in that the fusing point of high-melting-point Stereocomplex type polylactic acid used in this method is 227~244 DEG C, and used is low
The fusing point of fusing point Stereocomplex type polylactic acid is 185~213 DEG C.
5. the system of the high-performance stereocomplex PLA material according to claim 3 or 4 with superior low temperature mobility
Preparation Method, it is characterised in that high-melting-point Stereocomplex type polylactic acid used in this method is 30~90 parts, low melting point used
Stereocomplex type polylactic acid is 10~70 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910134444.7A CN109836790A (en) | 2019-02-23 | 2019-02-23 | High-performance stereocomplex PLA material with superior low temperature mobility and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164993A (en) * | 2008-09-29 | 2011-08-24 | 帝人株式会社 | Polylactic acid film |
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2019
- 2019-02-23 CN CN201910134444.7A patent/CN109836790A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164993A (en) * | 2008-09-29 | 2011-08-24 | 帝人株式会社 | Polylactic acid film |
Non-Patent Citations (1)
| Title |
|---|
| ZHENWEI LIU: "Stereocomplex-type polylactide with bimodal melting temperature distribution: Toward desirable melt-processability and thermomechanical performance", 《POLYMER》 * |
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Application publication date: 20190604 |