CN108659484B - Application of silicon dioxide in reduction of melt viscosity in polylactic acid melt processing process - Google Patents
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- CN108659484B CN108659484B CN201810253392.0A CN201810253392A CN108659484B CN 108659484 B CN108659484 B CN 108659484B CN 201810253392 A CN201810253392 A CN 201810253392A CN 108659484 B CN108659484 B CN 108659484B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 91
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 90
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 53
- 238000010128 melt processing Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 13
- 230000009467 reduction Effects 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000000155 melt Substances 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000945 filler Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses an application of silicon dioxide in reducing melt viscosity in the melt processing process of polylactic acid, polylactic acid and silicon dioxide particles are blended until the silicon dioxide particles are uniformly distributed in the polylactic acid, the adding volume of the silicon dioxide is 0-1% of the volume of the polylactic acid, the surface hydroxyl of the silicon dioxide is partially substituted by methyl, and the substitution proportion of the methyl is more than or equal to 50% according to mol; the silica particles are spherical and have a diameter of 10 to 30 nm. The invention effectively reduces the melt viscosity, has little influence on the mechanical property of the melt, and can improve the modulus or strength of the polylactic acid.
Description
The invention relates to a divisional application of parent application 'method for reducing the viscosity of polylactic acid melt and application thereof', wherein the parent application has the application number of 2015107306633, and the application date of 2015 is 10 months and 30 days.
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a method for reducing melt viscosity in a polylactic acid melting processing process.
Background
Polylactic acid (PLA) is a biodegradable polymer and is widely used in the fields of packaging materials and biomedicine. The melt viscosity of polylactic acid during melt processing has a significant influence on the shaping and the final properties of the material. The melt processing viscosity of the polylactic acid is effectively reduced without reducing other application properties of the material, so that the polylactic acid can be effectively prevented from being damaged due to the thermal stability problem in the melt processing process, and the processing energy consumption is reduced while the processing precision of the product is ensured. Particularly, the polylactic acid which is a biodegradable polymer with application prospect has more important significance for improving the processing performance.
In reducing the viscosity of a polymer material during melt processing to improve its processing flowability, conventional methods are often used to add an amount of plasticizer to the polymer material or to raise the processing temperature. Although the use of the plasticizer can significantly improve the melt processing fluidity of the polymer, the mechanical properties and the like of the product are negatively affected, and the migration of the plasticizer occurs to affect the use performance of the product with the lapse of time; simply raising the processing temperature is limited by the thermal stability of the polymer material being processed. Therefore, the conventional techniques for improving the flowability of polymer in melt processing inevitably lose some properties of the material in some aspects, and thus, there is a need for new techniques for improving the flowability of polymer in melt processing and molding, while overcoming the deficiencies of the conventional techniques.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the invention aims to provide a method for reducing the melt viscosity in the melt processing process of polylactic acid, which has little influence on the mechanical property and can improve the modulus or strength of the polylactic acid.
The purpose of the invention is realized by the following technical scheme:
the method for reducing the melt viscosity of the polylactic acid comprises the following steps: blending polylactic acid and silicon dioxide particles until the silicon dioxide particles are uniformly distributed in the polylactic acid, and naturally cooling to room temperature of 20-25 ℃, wherein:
the adding volume of the silicon dioxide is 0-1% of the volume of the polylactic acid by volume, namely more than 0 and less than or equal to 1%; the surface hydroxyl of the silicon dioxide is partially substituted by methyl, and the substitution ratio of the methyl is more than or equal to 50% according to the mol; the silicon dioxide particles are spherical and have the diameter of 10-30 nm; adopts melt blending at 150-200 ℃.
In the technical scheme, the weight average molecular weight of the polylactic acid is 10-15 ten thousand.
In the technical scheme, melt blending is adopted, and the blending time is 10-60 min, preferably 15-30 min.
In the technical scheme, melt blending is adopted, and the temperature is 170-180 ℃.
In the above technical solution, the diameter of the silica particles is 12-20 nm.
In the above technical scheme, the surface hydroxyl groups of the silica are partially substituted by methyl groups, and the substitution ratio of the methyl groups is 60 to 80% by mole.
In the technical scheme, the adding volume of the silicon dioxide is 0.1-0.7% of the volume of the polylactic acid by volume.
The method is applied to reducing the melt viscosity in the melt processing process of the polylactic acid, the polylactic acid with uniformly distributed silicon dioxide particles prepared by the method reduces the melt viscosity of the polylactic acid in the melt processing process, and the glass transition temperature and the mechanical property are not influenced.
The application of silicon dioxide in reducing melt viscosity in the melt processing process of polylactic acid, wherein the surface hydroxyl of the silicon dioxide is partially substituted by methyl, and the substitution proportion of the methyl is more than or equal to 50% according to the mol; the silica particles are spherical and have a diameter of 10 to 30 nm.
In the above technical solution, the diameter of the silica particles is 12-20 nm.
In the above technical scheme, the surface hydroxyl groups of the silica are partially substituted by methyl groups, and the substitution ratio of the methyl groups is 60 to 80% by mole.
The invention relates to a method for reducing the viscosity of polylactic acid melt by adding nano particles, wherein, the filler is introduced by melt blending after the polylactic acid raw material is dried, the filler needs to be a spherical nano silica particle filler with hydrophobic property on the surface after surface modification treatment, the hydrophobic property on the surface of the silica particle can be prepared by methyl substitution of hydroxyl on the original surface, for example, the hydroxyl on the surface of the silica particle is treated by dimethyldichlorosilane to obtain silica particles with methyl on the surface (reference: Honglifu, Jinxin, preparation and modification of superfine silica [ J ], Beijing university of chemical industry, 2004, 31(5):69-72), and the substitution ratio is adjusted to obtain silica particle fillers with different hydrophobic properties, and the particle size of the particle filler is preferably nano size, if the particle diameter is 12nm, the larger the particle size, the stronger the hydrophobicity of the surface can be controlled, for example, a silica particle filler with 50% of the surface hydroxyl groups substituted by methyl groups is selected. The method for reducing the melt viscosity in the polylactic acid melt processing process by adding the surface hydrophobic nano-sized silica particles is embodied in the typical melt processing process of melt blending for 15min at the melt processing temperature of 170 ℃ by controlling the rotating speed of a torque rheometer to be 32rpm, the glass transition temperature of the material is not influenced, the mechanical property of the material is not lost, the glass transition temperature and the mechanical property of the material are not reduced like adding a plasticizer, and the material is not further decomposed due to the fact that the melt fluidity is increased through high temperature.
Compared with the prior art, the technical method provided by the invention has the advantages of simple requirements and convenience in operation, and provides a simple and feasible method for reducing the melt viscosity during the melt processing of the polylactic acid. For this method, it is important to control the dispersion state of the silica particles added in melt blending in the polylactic acid, which is a measure for improving the dispersion state of the silica particle filler and for shortening the melt processing time as much as possible.
Drawings
FIG. 1 is a steady state shear flow diagram at 170 ℃ for a sample of polylactic acid and polylactic acid-silica blend of the present invention wherein □ represents pure PLA, and wherein □ represents the pure PLA, and wherein the &lTtT transition = O "&gTt &/T &gTt represents PLA/R0.1%,
represents PLA/R0.3%, ◇ represents PLA/R0.5%,
represents PLA/R0.7%.
FIG. 2 is a scanning electron microscope image of a sample of polylactic acid and polylactic acid-silica blend of the present invention at room temperature, wherein (a) represents pure polylactic acid, (b) represents a 1mm thick sheet sample prepared in example 1, and (c) represents a 1mm thick sheet sample prepared in example 2.
FIG. 3 is a graph of a second temperature ramp at a ramp rate of 10 deg.C/min for a sample of polylactic acid and polylactic acid-silica blends of the present invention using a differential scanning calorimeter, curve 1 representing PLA, curve 2 representing 0.1% PLA/R, and curve 3 representing 0.7% PLA/R.
FIG. 4 is a stress-strain curve at room temperature for samples of polylactic acid and polylactic acid-silica blends of the present invention, where curve 1 represents PLA, curve 2 represents PLA/R0.1%, and curve 3 represents PLA/R0.7%.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Polylactic acid purchased from SABIC Innovative plastics, original general electric company, and having a weight average molecular weight of 13 ten thousand 4800 and a density of 1.24g/cm according to GPC test3(ii) a The silica particle filler R974 is purchased from Evonik company, Prodegussa company (abbreviated as R974 or R), the particle diameter is 12-15 nm, and the methyl substitution ratio is 50%; the torque rheometer was purchased from Shanghai Korea corporation and is of the type: XSS-30; stress-controlled rotational rheometer purchased from TA, Inc. under the model of AR2000 with a controlled parallel plate spacing of 0.9mm, and was subjected to shear rate scanning at 170 deg.C to obtain a steady-state shear flow curve, wherein the shear rate scanning range was 0.01-40s-1(ii) a The scanning electron microscope is an S-4800 Hitachi field emission electron microscope; the model adopted by differential scanning calorimetry is Netzsch 204; an electric tensile machine is available from Testometric, UK under the model number M-350-20 KN.
Example 1
Taking 62g of PLA, weighing silica filler R974 with the volume accounting for 0.1 percent of the volume of the polylactic acid, drying for 24 hours at 60 ℃, putting into an internal mixing chamber of an XSS-30 torque rheometer with the temperature being set to 170 ℃, setting the rotating speed to be 32rpm, carrying out melt processing for 15min, taking out a sample, and cooling to the room temperature of 20-25 ℃, thus obtaining 0.1 percent of PLA/R.
Example 2
Taking 62g of PLA, weighing silica filler R974 with the volume accounting for 0.3 percent of the volume of the polylactic acid, drying for 24 hours at 60 ℃, putting into an internal mixing chamber of an XSS-30 torque rheometer with the temperature being set to 170 ℃, setting the rotating speed to be 32rpm, carrying out melt processing for 15min, taking out a sample, and cooling to the room temperature of 20-25 ℃, thus obtaining 0.3 percent of PLA/R.
Example 3
Taking 62g of PLA, weighing silica filler R974 with the volume accounting for 0.5 percent of the volume of the polylactic acid, drying for 24 hours at 60 ℃, putting into an internal mixing chamber of an XSS-30 torque rheometer with the temperature being set to 170 ℃, setting the rotating speed to be 32rpm, carrying out melt processing for 15min, taking out a sample, and cooling to the room temperature of 20-25 ℃, thus obtaining 0.5 percent of PLA/R.
Example 4
Taking 62g of PLA, weighing silica filler R974 with the volume accounting for 0.7 percent of the volume of the polylactic acid, drying for 24 hours at 60 ℃, putting into an internal mixing chamber of an XSS-30 torque rheometer with the temperature being set to 170 ℃, setting the rotating speed to be 32rpm, carrying out melt processing for 15min, taking out a sample, and cooling to the room temperature of 20-25 ℃, thus obtaining 0.7 percent of PLA/R.
Example 5
Taking 62g of PLA, weighing silica filler R974 with the volume accounting for 1% of the volume of the polylactic acid, drying at 60 ℃ for 24 hours, putting into an internal mixing chamber of an XSS-30 torque rheometer with the temperature set to 170 ℃, setting the rotating speed to be 32rpm, carrying out melt processing for 15min, taking out a sample, and cooling to room temperature of 20-25 ℃, thus obtaining PLA/R1.
The samples and the pure polylactic acid samples were tested by preheating the samples on a flat vulcanizing press for 4min at a temperature of 170 ℃ using a 1mm thick mold, melting the samples, pressing to 20Mpa at a rate of 0.1Mpa/min in a stepwise manner, and maintaining the pressure at 5, 10, and 20Mpa for 2min, respectively. And then transferring the sample to a cold pressing plate for pressure maintaining and shaping to obtain a thin sample with the thickness of 1mm formed by melting and hot pressing.
The distance between the parallel plates is controlled to be 0.9mm at 170 ℃ by using a stress control type rotary rheometerPerforming shear rate scanning under the condition to obtain a steady-state shear flow curve, wherein the shear rate scanning range is 0.01-40s-1The results are shown in FIG. 1, where □ denotes pure PLA, &lTtT translation = o "&gTt o &lTt/t &gTt denotes PLA/R0.1%,
represents PLA/R0.3%, ◇ represents PLA/R0.5%,
representing 0.7% PLA/R, an overall decrease in the viscosity curve compared to pure polylactic acid can be found, indicating that the addition of silica particulate filler particles can cause a decrease in the steady state viscosity.
The samples prepared in the above examples were cooled in liquid nitrogen for 30min, and then rapidly brittle-broken, randomly selected cross-sectional portions, gold-sprayed on the surface by a gold-spraying apparatus, and fixed for observation by a scanning electron microscope, and the results are shown in fig. 2, in which (a) represents a pure polylactic acid, (b) represents a 1mm thick sheet sample prepared in example 1, and (c) represents a 1mm thick sheet sample prepared in example 2, and thus it was found that although a certain aggregate having a size larger than that of primary particles is present and is not completely dispersed in the polylactic acid, the dispersion state of the filler is substantially good and no aggregate having a very large size is present.
By using a differential scanning calorimetry test, firstly heating and melting at 10 ℃/min, then cooling to room temperature at 10 ℃/min to obtain a glassy state sample of the sample, and then heating at 10 ℃/min, wherein the obtained sample differential scanning calorimetry curve is shown in figure 3, the curve 1 represents PLA, the curve 2 represents PLA/R0.1%, and the curve 3 represents PLA/R0.7%, so that the glass transition temperature of the sample is the same as that of pure polylactic acid and is not significantly influenced.
Further, the sample piece obtained by hot pressing is made into a dumbbell type sample, referring to GB/T1040-.
The samples of examples 2, 3 and 5 were tested by the same test means, and the results were substantially the same as in examples 1 and 4, and the loading of silica particles with different surface hydrophobicity in reducing the melt viscosity during the melt processing of polylactic acid was determined to have a critical value, and exceeding the critical loading caused the viscosity of the material to increase, especially the silica particles with weak surface hydrophobicity and strong hydrophilicity were filled with silica particles with a surface hydroxyl group of 50% substituted by methyl group and a particle diameter of 12nm, and the critical value was 1% by volume. When the filling amount is less than a certain critical volume fraction, the viscosity of the material has a minimum value along with the increase of the filling amount of the silicon dioxide, namely, the optimal filling amount of the silicon dioxide which can reduce the melt viscosity of the polylactic acid exists, and when the silicon dioxide particles with the particle diameter of 12nm and 50 percent of surface hydroxyl groups substituted by methyl are adopted for filling, the viscosity is obviously reduced at the filling amount of 0.1 percent of the volume fraction.
Referring to the preparation method and the test method in the above embodiments, the polylactic acid-silicon dioxide blend of the present invention can be prepared by adjusting the process parameters in the invention, and the blend shows properties of reduced melting point, basically maintained glass transition temperature and basically maintained mechanical properties after being tested.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. The application of the silicon dioxide in reducing the melt viscosity in the melting processing process of the polylactic acid is characterized in that the polylactic acid and the silicon dioxide particles are blended until the silicon dioxide particles are uniformly distributed in the polylactic acid, and the mixture is naturally cooled to the room temperature of 20-25 ℃, so that the melt viscosity of the polylactic acid is reduced, and the glass transition temperature and the mechanical property are not influenced; wherein: the adding volume of the silicon dioxide is 0.1-0.7% of the volume of the polylactic acid by volume; the surface hydroxyl of the silicon dioxide is partially substituted by methyl, and the substitution ratio of the methyl is more than or equal to 50% according to the mol; the silicon dioxide particles are spherical and have the diameter of 10-30 nm; adopts melt blending at 150-200 ℃.
2. Use of silica according to claim 1 for reducing the melt viscosity during melt processing of polylactic acid, wherein the silica particles have a diameter of 12-20 nm.
3. Use of a silica according to claim 1 for reducing the melt viscosity during melt processing of polylactic acid, wherein the surface hydroxyl groups of the silica are partially substituted by methyl groups, the proportion of methyl groups being 60 to 80% by mole.
4. Use of silica according to claim 1 for reducing the melt viscosity during melt processing of polylactic acid, wherein the polylactic acid has a weight average molecular weight of 10 to 15 ten thousand.
5. The use of silica according to claim 1 for reducing the melt viscosity during melt processing of polylactic acid, wherein melt blending is used for a time of 10 to 60 min.
6. Use of a silica according to claim 5 for reducing the melt viscosity during melt processing of polylactic acid, wherein the blending time is 15-30 min.
7. The use of silica according to claim 1 for reducing the melt viscosity during melt processing of polylactic acid, wherein melt blending is used at a temperature of 170-180 ℃.
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| JP3409609B2 (en) * | 1996-10-14 | 2003-05-26 | 凸版印刷株式会社 | Easy-adhesion stretched polylactic acid sheet |
| CN100497478C (en) * | 2007-02-02 | 2009-06-10 | 浙江大学 | Method of preparing polylactic acid/silicon dioxide nano composite material from acidic silicasol |
| CN101519526A (en) * | 2008-10-10 | 2009-09-02 | 兰州理工大学 | Method for preparing polylactic acid/nanometer silicon dioxide composite material |
| ITMI20111273A1 (en) * | 2011-07-08 | 2013-01-09 | Fond Cariplo | BRILLIANT POLYMERS OF LACTIC ACID WITH HIGH VISCOSITY IN THE MOLTEN AND HIGH SHEAR SENSITIVITY AND THEIR Dwarf COMPOSITE |
| JP5882712B2 (en) * | 2011-12-12 | 2016-03-09 | 第一工業製薬株式会社 | Polylactic acid resin composition and resin molded body thereof |
| CN104788933B (en) * | 2015-05-08 | 2016-06-29 | 郑州大学 | A kind of preparation method of polymer/SiO2 nano composite material |
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| JP2000178346A (en) * | 1998-12-18 | 2000-06-27 | Kanebo Ltd | Expandable resin composition having biodegradability |
| CN102243448A (en) * | 2010-05-12 | 2011-11-16 | 株式会社理光 | Toner, development agent, and image forming method |
| WO2013186778A1 (en) * | 2012-06-13 | 2013-12-19 | Tipa Corp. Ltd | Biodegradable sheet |
| CN102719065A (en) * | 2012-07-06 | 2012-10-10 | 华东理工大学 | Polylactic acid/shear thickening fluid high-toughness material and preparation method |
| CN104072722A (en) * | 2014-07-08 | 2014-10-01 | 华东理工大学 | Shear thickening fluid microcapsule, reinforced high molecular material and preparation method and application of shear thickening fluid microcapsule and reinforced high molecular material |
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