CN106633707B - Reduce the method and its application of polylactic acid melt viscosity - Google Patents
Reduce the method and its application of polylactic acid melt viscosity Download PDFInfo
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- CN106633707B CN106633707B CN201510730663.3A CN201510730663A CN106633707B CN 106633707 B CN106633707 B CN 106633707B CN 201510730663 A CN201510730663 A CN 201510730663A CN 106633707 B CN106633707 B CN 106633707B
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 97
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 239000008187 granular material Substances 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 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
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 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
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 238000010094 polymer processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses the method and its application for reducing polylactic acid melt viscosity, it carries out polylactic acid and silica dioxide granule to be blended into silica dioxide granule being uniformly distributed in polylactic acid, by volume, the addition volume of silica is 0-the 1% of polylactic acid volume, the surface hydroxyl of silica is replaced by methyl moiety, according to a mole meter, the substitute proportion of methyl is more than or equal to 50%；Spherical, a diameter of 10-30nm is presented in silica dioxide granule.The present invention effectively reduces melt viscosity, little to its Effect on Mechanical Properties, while can also improve polylactic acid modulus or intensity.
Description
Technical field
The invention belongs to field of material preparation, melt is viscous during relating in particular to a kind of reduction polylactic acid melt-processed
The method of degree.
Background technology
Polylactic acid (Polylactic acid, PLA) is a kind of biodegradable polymer, in packaging material and biology
Medical domain is widely used.Melt viscosity of polylactic acid during melt-processed has weight for the final performance of molding and material
It influences.Other application performance of its melt-processed viscosity without reducing material is effectively reduced, polylactic acid is not only can effectively avoid
Because being destroyed caused by thermal stability problems during melt-processed, and more while ensureing product processing precise degree
Reduce power consumption of polymer processing.Especially polylactic acid is this carries out for the biodegradable polymer for having application prospect, improves it and adds
Work performance more has especially important meaning.
Reduce molten polymer material processing when viscosity to promote its processing fluidity in terms of, frequently with tradition side
Method is that a certain amount of plasticizer or raising processing temperature are added into polymer material.Although the use of plasticizer can significantly change
The melt-processed mobility of kind polymer, but mechanical property of product etc. can become negatively affected, and over time,
It also occur that migration of plasticizer and influence the performance of product；The simple processing temperature that increases is then by institute's processable polymer
The restriction of material thermal stability.Therefore, tradition promotes these technical methods of polymer melting processing fluidity, total inevitable
Ground can loss material in some aspects properties, thus, be badly in need of to promote in polymer melting machine-shaping field poly-
Polymer melt processing fluidity, and the insufficient new technology of conventional method can be overcome simultaneously.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art, and it is molten that the object of the present invention is to provide a kind of reduction polylactic acid
Melt the method for melt viscosity in process, this method is little to its Effect on Mechanical Properties, while can also improve polylactic acid mould
Amount or intensity.
The purpose of the present invention is achieved by following technical proposals：
The method for reducing polylactic acid melt viscosity, carries out as steps described below：Polylactic acid and silica dioxide granule are carried out
It is blended into silica dioxide granule to be uniformly distributed in polylactic acid, 20-25 degrees Celsius of cooled to room temperature, wherein：
By volume, the addition volume of silica is 0-the 1% of polylactic acid volume, that is, is more than 0 and is less than or equal to 1%；
The surface hydroxyl of silica is replaced by methyl moiety, and according to a mole meter, the substitute proportion of methyl is more than or equal to 50%；Titanium dioxide
Spherical, a diameter of 10-30nm is presented in silicon particle；Using melt blending, temperature is 150-200 degrees Celsius.
In the above-mentioned technical solutions, the weight average molecular weight of the polylactic acid is 10 ten thousand -15 ten thousand.
In the above-mentioned technical solutions, using melt blending, the blending time is 10-60min, preferably 15-30min.
In the above-mentioned technical solutions, using melt blending, temperature is 170-180 degrees Celsius.
In the above-mentioned technical solutions, a diameter of 12-20nm of silica dioxide granule.
In the above-mentioned technical solutions, the surface hydroxyl of silica is replaced by methyl moiety, and according to a mole meter, methyl takes
It is 60-80% for ratio.
In the above-mentioned technical solutions, by volume, the addition volume of silica is 0.1-the 0.7% of polylactic acid volume.
Application of above method during reducing polylactic acid melt-processed in melt viscosity is prepared by the above method
The polylactic acid of silica dioxide granule is uniformly distributed during melt-processed, reduces polylactic acid melt viscosity, and keep vitrifying
Transition temperature and mechanical property are unaffected.
Application of silica during reducing polylactic acid melt-processed in melt viscosity, the wherein surface of silica
Hydroxyl is replaced by methyl moiety, and according to a mole meter, the substitute proportion of methyl is more than or equal to 50%；Ball is presented in silica dioxide granule
Shape, a diameter of 10-30nm.
In the above-mentioned technical solutions, a diameter of 12-20nm of silica dioxide granule.
In the above-mentioned technical solutions, the surface hydroxyl of silica is replaced by methyl moiety, and according to a mole meter, methyl takes
It is 60-80% for ratio.
The present invention is a kind of method reducing polylactic acid melt viscosity by adding nano-particle, wherein by polylactic acid
The filler introduced by melt blending after raw material drying, the filler need to be a kind of hydrophobic by surface modification processing rear surface presentation
The spherical nano-silicon dioxide granular filler of characteristic, the hydrophobic properties of silica particles can be by by original surface
On hydroxyl carry out methyl substitution and prepared, such as with dimethyldichlorosilane to silica surface hydroxyl at
Reason obtains the silicon dioxide granule (bibliography that methyl is contained on surface：The preparation of Hong Lifu, Jin Xin superfine silicon dioxides with change
Property [J] Beijing University of Chemical Technology journal, 2004,31 (5):69-72), and the adjustment of substitute proportion is carried out, it is different hydrophobic to obtain
The silica dioxide granule filler of characteristic, and the particle size of granular filler is preferred with nano-scale, if particle diameter is 12nm,
It can control its surface hydrophobic strong when particle size is bigger than normal, such as the titanium dioxide after selecting the 50% of surface hydroxyl to be replaced by methyl
Silicon particle filler.The present invention is advocated molten to reduce polylactic acid by adding surface hydrophobic nano-size silica particles
The method for melting melt viscosity in process passes through the rotating speed of control torque rheometer at being 170 DEG C in melt processing temperature
It is embodied in the Typical melt process of 32rpm melt blendings 15min, and the glass transition temperature of material is not by shadow
It rings, the mechanical property of material is not lost, and glass transition temperature and the reduction of material will not be reduced as being added plasticizer
Mechanical property will not cause the further decomposition of material because of fluidity of molten is increased by high temperature.
Compared with prior art, technical method provided by the present invention requires simple, operation facility, molten to reduce polylactic acid
Melt viscosity when melting processing provides a kind of simple and practicable method.For this method, two are added in melt blending
Dispersity control of the silicon oxide particle in polylactic acid is critically important, is conducive to improve silica dioxide granule filler dispersity
The time of measure and melt-processed as short as possible.
Description of the drawings
Fig. 1 is the steady state shearing stream of the polylactic acid and polylactic acid-silica blend sample of the present invention at 170 DEG C
Cardon, wherein indicate pure PLA, and zero indicates PLA/R0.1%,Indicate that PLA/R0.3%, ◇ indicate PLA/R0.5%,Table
Show PLA/R0.7%.
Fig. 2 is the polylactic acid and polylactic acid-scanning electron microscopy of the silica blend sample in room temperature of the present invention
Mirror figure (b) indicates the 1mm thickness chip samples obtained by embodiment 1, (c) indicates 2 institute of embodiment wherein (a) indicates pure polylactic acid
1mm thickness chip sample obtained.
Fig. 3 be the present invention polylactic acid and polylactic acid-silica blend sample under the heating rate of 10 DEG C/min
Second of the temperature-rise period figure tested with differential scanning calorimeter, curve 1 indicate that PLA, curve 2 indicate PLA/R0.1%, curve 3
Indicate PLA/R0.7%.
Fig. 4 is that the stress-strain of the polylactic acid and polylactic acid-silica blend sample of the present invention in room temperature is bent
Line, wherein curve 1 indicate that PLA, curve 2 indicate that PLA/R0.1%, curve 3 indicate PLA/R0.7%.
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific embodiment.
Polylactic acid purchase innovates plastics in SABIC, and former General Electric Co. Limited is 130,000 through GPC test weight average molecular weight
4800, density 1.24g/cm3；In Evonik companies, former goldschmidt chemical corporation (is abbreviated as the R974 purchases of silica dioxide granule filler
R974 or R), particle diameter is 12-15nm, and methyl substitute proportion is 50%；Torque rheometer is bought in Shanghai KeChuang Co., Ltd,
Its model：XSS-30；Stress Control type rotational rheometer is bought between TA companies, model AR2000, control parallel-plate
Away from for 0.9mm, under the conditions of 170 DEG C carrying out shearing rate scan obtains steady state shearing flow curve, the scanning model of shear rate
It encloses for 0.01-40s-1；Scanning electron microscope is S-4800 Hitachis field emission type electron microscope；Differential scanning calorimetry uses
Model Netzsch 204；Electronic tensile machine is bought in testometric companies of Britain, model M-350-20KN.
Embodiment 1
PLA 62g are taken, by volume, the addition volume of silica weighs silica for the 0.1% of polylactic acid volume
Filler R974 is dried 24 hours at 60 DEG C, is put into the banburying chamber that temperature is set as 170 DEG C of XSS-30 torque rheometers, if
It is 32rpm, melt-processed 15min to determine rotating speed, takes out sample and is cooled to 20-25 degrees Celsius of room temperature to get to PLA/
R0.1%.
Embodiment 2
PLA 62g are taken, by volume, the addition volume of silica weighs silica for the 0.3% of polylactic acid volume
Filler R974 is dried 24 hours at 60 DEG C, is put into the banburying chamber that temperature is set as 170 DEG C of XSS-30 torque rheometers, if
It is 32rpm, melt-processed 15min to determine rotating speed, takes out sample and is cooled to 20-25 degrees Celsius of room temperature to get to PLA/
R0.3%.
Embodiment 3
PLA 62g are taken, by volume, the addition volume of silica weighs silica for the 0.5% of polylactic acid volume
Filler R974 is dried 24 hours at 60 DEG C, is put into the banburying chamber that temperature is set as 170 DEG C of XSS-30 torque rheometers, if
It is 32rpm, melt-processed 15min to determine rotating speed, takes out sample and is cooled to 20-25 degrees Celsius of room temperature to get to PLA/
R0.5%.
Embodiment 4
PLA 62g are taken, by volume, the addition volume of silica weighs silica for the 0.7% of polylactic acid volume
Filler R974 is dried 24 hours at 60 DEG C, is put into the banburying chamber that temperature is set as 170 DEG C of XSS-30 torque rheometers, if
It is 32rpm, melt-processed 15min to determine rotating speed, takes out sample and is cooled to 20-25 degrees Celsius of room temperature to get to PLA/
R0.7%.
Embodiment 5
PLA 62g are taken, by volume, the addition volume of silica weighs silica for the 1% of polylactic acid volume and fills out
Expect R974, dried 24 hours at 60 DEG C, be put into the banburying chamber that temperature is set as 170 DEG C of XSS-30 torque rheometers, sets
Rotating speed is 32rpm, melt-processed 15min, takes out sample and is cooled to 20-25 degrees Celsius of room temperature to get to PLA/R1%.
Above-mentioned sample and pure polylactic acid sample are tested, using 1mm thickness molds, keep sample pre- on vulcanizing press
Hot 4min, preheating temperature are 170 DEG C, make its melting, 20Mpa is then pressed onto in a manner of gradually pressurizeing, compression rate is
0.1Mpa/min, and keep pressure 2min respectively at 5,10,20Mpa.Then pressurize on cold pressing plate is transferred the sample into shape,
Obtain the 1mm thickness chip samples that melting heat is pressed into.
Using Stress Control type rotational rheometer, parallel plate spacing 0.9mm is controlled, shearing speed is carried out under the conditions of 170 DEG C
Rate scans, and obtains steady state shearing flow curve, the scanning range of shear rate is 0.01-40s-1, as a result as shown in fig. 1,
Middle indicates pure PLA, and zero indicates PLA/R0.1%,Indicate that PLA/R0.3%, ◇ indicate PLA/R0.5%,Indicate PLA/
R0.7% is compared with pure polylactic acid, it can be found that whole decline occurs for viscograph, this shows that adding silica dioxide granule fills out
Expect particle, the reduction of steady-state viscosity can be caused.
Sample prepared by above-described embodiment is put into liquid nitrogen cooling 30min, then rapid brittle failure selects to break to randomness
Face part is handled in this surface metal spraying using metal-spraying equipment, then is observed for scanning electron microscope after being fixed, as a result such as
Shown in Fig. 2, (a) indicates pure polylactic acid, (b) indicates the 1mm thickness chip samples obtained by embodiment 1, (c) indicates 2 institute of embodiment
1mm thickness chip sample obtained, it can be seen that, although there is certain aggregation that size is more than primary particle in filler, not
It is completely dispersed in polylactic acid, but its dispersity is substantially good, has no that very large-sized aggregation exists.
Tested using differential scanning calorimetry, first with 10 DEG C/min heat up melt, after cool to room temperature with 10 DEG C/min and obtain
It heats up to the glassy state sample of sample, then with 10 DEG C/min, in obtained sample differential scanning calorimetry curve such as Fig. 3
Shown, curve 1 indicates that PLA, curve 2 indicate that PLA/R0.1%, curve 3 indicate PLA/R0.7%, it is seen that its glass transition temperature
Degree is not subject to a significant impact as pure polylactic acid.
Dumbbell shape sample further is made in the print that hot pressing obtains, with reference to GB/T 1040-2006, using electronics pulling force
Machine controls extension test rate for 2mm/min, Sample Width 6.5mm, gauge length 30mm, in obtained stress strain curve such as Fig. 4
Shown, wherein curve 1 indicates that PLA, curve 2 indicate that PLA/R0.1%, curve 3 indicate PLA/R0.7%, the tensile strength of material
Being compared with pure polylactic acid with stretch modulus does not reduce, tensile yield behavior also without significant change, only elongation at break
Reduce.
The sample of embodiment 2,3,5 is tested using same test means, it is as a result essentially identical with embodiment 1 and 4,
During reducing polylactic acid melt-processed in terms of melt viscosity, the used hydrophobic silica dioxide granule filling of different surfaces
There are a critical values for amount, viscosity of material can be caused to transfer to increase more than this critical loading, especially particulate surface hydrophobic is weak
And the silica dioxide granule that hydrophily is strong, the particle diameter after using the 50% of surface hydroxyl to be replaced by methyl is the dioxy of 12nm
Silicon carbide particle is filled, and critical value is volume fraction 1%.When loading is less than certain critical volume fraction, with titanium dioxide
The increase of silicon loading, there are a minimum values for the viscosity of material, that is, having one optimal makes polylactic acid melt viscosity drop
Low silica-filled amount, the particle diameter after using the 50% of surface hydroxyl to be replaced by methyl is the silica of 12nm
Can be to find that viscosity is substantially reduced at volume fraction 0.1% in its loading when grain filling.
With reference to the preparation method and test method in above-described embodiment, it is adjusted according to technological parameter in invention content,
Polylactic acid-silica blend in the present invention can be prepared, blend, which becomes, after tested reveals fusing point decline, vitrifying
The property that transition temperature and mechanical property remain unchanged substantially.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (9)
1. the method for reducing polylactic acid melt viscosity, which is characterized in that carry out as steps described below：By polylactic acid and silica
Particle carries out being blended into silica dioxide granule to be uniformly distributed in polylactic acid, 20-25 degrees Celsius of cooled to room temperature, wherein：
By volume, the addition volume of silica is 0-the 1% of polylactic acid volume, that is, is more than 0 and is less than or equal to 1%；Dioxy
The surface hydroxyl of SiClx is replaced by methyl moiety, and according to a mole meter, the substitute proportion of methyl is more than or equal to 50%；Silica
Spherical, a diameter of 10-30nm is presented in grain；Using melt blending, temperature is 150-200 degrees Celsius.
2. it is according to claim 1 reduce polylactic acid melt viscosity method, which is characterized in that silica dioxide granule it is straight
Diameter is 12-20nm.
3. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that the surface hydroxyl of silica
Base is replaced by methyl moiety, and according to a mole meter, the substitute proportion of methyl is 60-80%.
4. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that by volume, titanium dioxide
The addition volume of silicon is 0.1-the 0.7% of polylactic acid volume.
5. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that the weight of the polylactic acid is equal
Molecular weight is 10 ten thousand -15 ten thousand.
6. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that use melt blending, altogether
It does time as 10-60min.
7. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that use melt blending, altogether
It does time as 15-30min.
8. the method according to claim 1 for reducing polylactic acid melt viscosity, which is characterized in that use melt blending, temperature
Degree is 170-180 degrees Celsius.
9. application of method during reducing polylactic acid melt-processed in melt viscosity as described in one of claim 1-8,
It is characterized in that, the polylactic acid for being uniformly distributed silica dioxide granule prepared reduces polylactic acid melt during melt-processed
Viscosity, and keep glass transition temperature and mechanical property unaffected.
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|---|---|---|---|
| CN201810253392.0A CN108659484B (en) | 2015-10-30 | 2015-10-30 | Application of silicon dioxide in reduction of melt viscosity in polylactic acid melt processing process |
| CN201510730663.3A CN106633707B (en) | 2015-10-30 | 2015-10-30 | Reduce the method and its application of polylactic acid melt viscosity |
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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 |
| JP3787447B2 (en) * | 1998-12-18 | 2006-06-21 | 株式会社カネカ | Expandable resin composition having biodegradability |
| 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 |
| JP2011237663A (en) * | 2010-05-12 | 2011-11-24 | Ricoh Co Ltd | Toner, developer and image forming method |
| 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 |
| EP2861424A4 (en) * | 2012-06-13 | 2015-09-09 | 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 |
| CN104072722B (en) * | 2014-07-08 | 2016-11-02 | 华东理工大学 | Shear thickening fluid microcapsule, Polymer Toughening and its preparation method and application |
| 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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- 2015-10-30 CN CN201510730663.3A patent/CN106633707B/en active Active
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| CN108659484B (en) | 2020-04-17 |
| CN106633707A (en) | 2017-05-10 |
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