CN108340529B - A method of pressurization prepares amorphous polylactic acid plate at a slow speed - Google Patents
A method of pressurization prepares amorphous polylactic acid plate at a slow speed Download PDFInfo
- Publication number
- CN108340529B CN108340529B CN201810137180.6A CN201810137180A CN108340529B CN 108340529 B CN108340529 B CN 108340529B CN 201810137180 A CN201810137180 A CN 201810137180A CN 108340529 B CN108340529 B CN 108340529B
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- poly
- pressurization
- plate
- amorphous polylactic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5808—Measuring, controlling or regulating pressure or compressing force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5816—Measuring, controlling or regulating temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention provides a kind of method that pressurization prepares amorphous polylactic acid plate at a slow speed, by polylactic acid raw material heating melting, then dwell pressure is forced into certain speed, room temperature is down in pressure maintaining period, last release obtains amorphous polylactic acid plate, heating melting temperature is 175 DEG C ~ 195 DEG C, pressing speed 200MPa/min-1000MPa/min, dwell pressure 250MPa-1000MPa.The present invention overcomes the technology prejudice that Quick-pressurizing prepares amorphous high molecular material, significantly reduce pumping rate and dwell pressure, meet the demand of industrial applications.
Description
Technical field
The invention belongs to amorphous polylactic acid preparation technical fields, and in particular to pressurization prepares amorphous polylactic acid plate to one kind at a slow speed
The method of material.
Background technique
As the increasingly depleted and environmental pollution of petroleum-based energy increasingly sharpens, how sustainable development becomes current for society
The major issue that the world faces.In the case where advocating energy-saving and emission-reduction and developing the background of low-carbon economy, researcher is more mesh
Light has invested biodegradable, environment amenable high molecular material.Therefore, environmental-friendly plastic substitution petroleum base is developed
Plastics have great importance.
Polylactic acid (PLA) belongs to aliphatic polyester compound, its synthesis material is renewable crop (lactic acid), does not depend on stone
Oil, and it is discarded after can biodegrade Cheng Shui and carbon dioxide, it is free from environmental pollution.Polylactic acid includes left-handed poly (l-lactic acid)
(PLLA), the poly- D-ALPHA-Hydroxypropionic acid of dextrorotation (PDLA) and the poly- D of racemic, Pfansteihl (PDLLA) are led in medical, industrial packaging and weaving etc.
Domain, it is general to select Poly L-lactic acid and poly- L-lactic acid.Poly L-lactic acid and poly- L-lactic acid are thermoplastic crystalline polymerization
Object, for crystallinity up to 60%, the transparency is poor, it is difficult to obtain amorphous plate, limit it and lead in medical instrument and industrial packaging etc.
The application in domain.
Amorphous polylactic acid can be obtained by melting-quenching method, but the process is limited by thermal conductivity, at most may be used
The amorphous plate of 2-3mm thickness is prepared, and at least needs the cooling rate of 200 DEG C/s-300 DEG C/s in preparation process, technique is multiple
Miscellaneous, uniform thickness is difficult to control.Although by add other macromolecule raw materials carry out modification amorphous plate can be obtained, other
The addition of macromolecule raw material can generate the problems such as environmental protection, recycling relatively, lose the environmental-friendly characteristic of poly-lactic acid material.
Zhang Rui waits quietly preparing amorphous polylactic acid plate using Quick-pressurizing, method particularly includes: after polylactic acid raw material melting, In
It from 0.1GPa Quick-pressurizing to 2.0GPa in 20ms, keeps pressure constant, is cooled to room temperature, sample, thickness of sample are taken out in release
For 1mm (" the isothermal cold crystallization behavioral study that Quick-pressurizing prepares amorphous polylactic acid ", Zhang Ruijing, Shao Chunguang, Li Qian, Wang Mingyou,
Open beans beans, Zhang Yang, Liu Chenggang, Hong Shiming, Shen Changyu).
For crystalline polymer material, in the preparation process of its amorphous product, researcher generallys use quick increasing
Platen press, pumping rate must reach 100GPa/s or more, and dwell pressure must also maintain 2.0GPa or more, could generate enough
Degree of supercooling, and then macromolecular chain is caused to freeze not crystallizing, this be prepare amorphous high molecular material common technology (1, Yuan,
C.S.,Hong,S.M.,Li,X.X.,Shen,R.,He,Z.,Lv,S.J.,...&Xi,D.K.(2011).Journal of
Physics D:Applied Physics,44(16),165405；2,Hong,S.M.,Liu,X.R.,Su,L.,Huang,
D.H. , &Li, L.B. (2006) ..Journal of Physics D:Applied Physics, 39 (16), 3684.), it is aforementioned
Document is also this principle.Although but it can obtain amorphous polylactic acid plate, however it remains following two large problems: (1) preparing
Need the pumping rate of 6000GPa/min and the dwell pressure of 2GPa in the process, condition is harsh, and so high pumping rate and
Dwell pressure can only reach in laboratory research, be difficult to realize industrial production at all；(2) the amorphous polylactic acid plate being prepared
Material is with a thickness of 1mm, finite thickness, it is difficult to meet diversified practical application request.Therefore, amorphous polylactic acid board industry
Development and utilization is still a great problem.
Summary of the invention
The present invention must use the technology prejudice of Quick-pressurizing for the preparation of amorphous polylactic acid plate in the prior art, provide
A method of pressurization prepares amorphous polylactic acid plate at a slow speed, overcome Quick-pressurizing prepare amorphous high molecular material technology it is inclined
See, significantly reduce pumping rate and dwell pressure, meets the demand of industrial applications.
The present invention adopts the following technical scheme:
A method of pressurization prepares amorphous polylactic acid plate at a slow speed, by polylactic acid raw material heating melting, then with certain
Speed is forced into dwell pressure, and room temperature is down in pressure maintaining period, and last release obtains amorphous polylactic acid plate, heating melting temperature
It is 175 DEG C~195 DEG C, pressing speed 200MPa/min-1000MPa/min, dwell pressure 250MPa-1000MPa；This hair
Bright needs guarantee to be down to room temperature during pressure maintaining, dwell time or rate of temperature fall are not particularly limited, for just
In industrial production, the preferred dwell time is 0.25-1h.
Preferably, the pressing speed is 300MPa/min-500MPa/min, dwell pressure 400MPa-500MPa.
Preferably, the amorphous polylactic acid plate with a thickness of 1mm-10mm.
Preferably, in the stress-relief process, release speed is less than 100MPa/min.
Preferably, polylactic acid raw material first carries out vacuum drying pretreatment before the heating melting.
Preferably, the polylactic acid raw material is Poly L-lactic acid, poly- L-lactic acid or Poly L-lactic acid and poly- L-lactic acid
The mixture of arbitrary proportion mixing.
Beneficial effects of the present invention are as follows:
(1) Quick-pressurizing method is the common technology for preparing amorphous high molecular material, principle be by fusing sample into
Row Fast Compression, and then enough degree of supercoolings are obtained, make macromolecular chain quick freezing and inhibits to crystallize.The present invention is used and is pressed at a slow speed
Cause prepares non-crystalline material, prepare non-crystalline material with Quick-pressurizing the difference is that, greatly reduce the pumping rate of preparation
And pressure.It is considered that causing in solidification process in pressure, the effect of pressure is greater than pumping rate, and at a slow speed in pressurization, pressure subtracts
The small volume of polylactic acid, increases the viscosity of substance, limits the movement of strand；Meanwhile during pressure causes at a slow speed, pressure
Power is effectively increased a large amount of nucleation of strand, it is suppressed that its speed of growth and form amorphous, this point and Quick-pressurizing system
Standby amorphous is entirely different in formation basic theory.Therefore, preparing amorphous product the present invention overcomes crystalline polymer material must
The technology prejudice that Quick-pressurizing method must be used, uses polylactic acid for raw material, the method by being pressurized at a slow speed, causes solidification using pressure
Principle overcomes the crystallization of polylactic acid, prepares a kind of completely amorphous polylactic acid plate；In particular, pumping rate is by 6000GPa/
Min is down to 200MPa/min-1000MPa/min, this does not mean only that pumping rate has reached the reduction of 3 to 4 orders of magnitude, more
Mean that the preparation of amorphous polylactic acid plate is strided forward from laboratory research to the big step of industrialized production, it is poly- to open amorphous at one stroke
The gate of lactic acid plate development and application！
(2) simultaneously under study for action, inventor surprisingly has found, by means of the present invention, amorphous polylactic acid plate thickness
It has been more than the thickness of the prior art, it is seen then that the thickness of amorphous polylactic acid plate prepared by the present invention has been more than the prior art, is belonged to
The new varieties of poly-lactic acid products, application prospect are more wide；
(3) method that the present invention prepares amorphous polylactic acid plate, it is simple and easy to operate, time-consuming is short, low energy consumption, synthesis cost
It is low, meet the production cost requirement of industrial applications, and do not need other additives in preparation process, does not destroy the ring of polylactic acid
The characteristic of border friendly；
(4) shape of preparation method according to the present invention, amorphous polylactic acid plate can be customized as needed, thus be made
Polylactic acid plate the fields such as medicine, industrial packaging and automobile with good application prospect.
Detailed description of the invention
Fig. 1 is the XRD diagram for the polylactic acid plate that embodiment 1 obtains.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, with reference to the accompanying drawing and specifically
Embodiment is further illustrated technical solution of the present invention.
Embodiment 1
A kind of preparation method of amorphous polylactic acid plate, comprising the following steps: by weight average molecular weight be 100,000 gather it is left-handed
Lactic raw material, which is placed in a vacuum drying oven, to be dried to remove moisture therein, and vacuum drying condition is 80 DEG C, -0.05MPa,
Drying time is 24 hours, and then the Poly L-lactic acid raw material after drying is placed in mold, and wherein mold is hollow square
Mold (raw material containing Poly L-lactic acid) is placed on flat-bed press, to Poly L-lactic acid by (side length 50mm, with a thickness of 5mm)
180 DEG C are heated to, melts Poly L-lactic acid completely, the Poly L-lactic acid of melting is carried out with the pumping rate of 200MPa/min
It is forced into 300MPa, while keeping constant pressure 300MPa, is cooled to 40 DEG C hereinafter, the dwell time is 0.5h, then with 100MPa/
The speed unloading pressure of min obtains the square plate sample with a thickness of 4.7mm to 0.1MPa；By gained square plate sample into
Row XRD tests structure, the result is shown in Figure 1, it can be seen that the rectangular board samples are non crystalline structure.
Embodiment 2
A kind of preparation method of amorphous polylactic acid plate, comprising the following steps: the poly- dextrorotation for being 100,000 by weight average molecular weight
Lactic raw material, which is placed in a vacuum drying oven, to be dried to remove moisture therein, and vacuum drying condition is 80 DEG C, -0.05MPa,
Drying time is 24 hours, and then the poly- L-lactic acid raw material after drying is placed in mold, and wherein mold is hollow positive triangle
Mold (containing poly- L-lactic acid raw material) is placed on flat-bed press by shape (side length 30mm, with a thickness of 8mm), to poly- dextrorotation cream
Acid is heated to 175 DEG C, melts poly- L-lactic acid completely, to the poly- L-lactic acid of melting with the pumping rate of 400MPa/min into
Row is forced into 500MPa, while keeping constant pressure 500MPa, is cooled to 40 DEG C hereinafter, the dwell time is 0.25h, then with
The speed unloading pressure of 100MPa/min obtains the equilateral triangle board samples with a thickness of 7.8mm to 0.1MPa；By gained positive three
Angular board samples carry out XRD test, which is non crystalline structure.
Embodiment 3
A kind of preparation method of amorphous polylactic acid plate, comprising the following steps: be a 200000 poly- left side by weight average molecular weight
Lactic acid/poly- L-lactic acid mixed raw material is revolved, mixed raw material is placed in a vacuum drying oven does first by mass ratio 1:1
Dry to remove moisture therein, vacuum drying condition is 80 DEG C, -0.05MPa, and drying time is 24 hours, then will be after drying
Polylactic acid mixed raw material be placed in mold, wherein mold be hollow circular (diameter 50mm, with a thickness of 10mm), by mold
(mixed raw material containing polylactic acid) is placed on flat-bed press, to polylactic acid mixed material heating to 190 DEG C, keeps polylactic acid mixture complete
Full-fusing is carried out being forced into 600MPa with the pumping rate of 800MPa/min, keeps constant pressure to the polylactic acid mixed raw material of melting
While 600MPa, 40 DEG C are cooled to hereinafter, the dwell time is 0.5h, then extremely with the speed unloading pressure of 100MPa/min
0.1MPa obtains the round board samples with a thickness of 9.8mm；Gained circle board samples are subjected to XRD test, the circle plate
Sample is non crystalline structure.
Embodiment 4
A kind of preparation method of amorphous polylactic acid plate, comprising the following steps: be a 160000 poly- left side by weight average molecular weight
Rotation lactic raw material, which is placed in a vacuum drying oven, to be dried to remove moisture therein, vacuum drying condition is 80 DEG C ,-
0.05MPa, drying time are 24 hours, and then the Poly L-lactic acid raw material after drying is placed in mold, during wherein mold is
Empty rectangle (a length of 20mm, width 10mm, with a thickness of 4mm), is placed in flat-bed press for mold (raw material containing Poly L-lactic acid)
On, 180 DEG C are heated to Poly L-lactic acid raw material, melts Poly L-lactic acid raw material completely, left-handed rotation lactic acid is gathered to melting
Be forced into 1000MPa with the pumping rate of 1000MPa/min, while keeping constant pressure 1000MPa, be cooled to 40 DEG C with
Under, dwell time 1.0h obtains the circle with a thickness of 3.6mm then with the speed unloading pressure of 100MPa/min to 0.1MPa
Shape board samples；Gained circle board samples are subjected to XRD test, which is non crystalline structure.
Performance test
Using preparation method of the invention, inventor is further to (i.e. different polylactic acid raw material classes under different technology conditions
Type and weight average molecular weight, heating temperature, pumping rate and dwell pressure) gained board samples phase structure be determined,
Related test results statistics such as the following table 1:
Board samples phase structure measurement result under 1 different technology conditions of table
To known to upper table analysis: amorphous polylactic acid plate is prepared substantially not by raw material left or right rotation type and Weight-average molecular
The influence of amount, and the thickness of plate is up to 10mm；But when heating melting temperature too low (< 175 DEG C), pumping rate it is too small (<
200MPa/min) or when dwell pressure too small (< 250MPa), pressure causes the crystallization that polylactic acid cannot be completely inhibited in process of setting,
The polylactic acid sample caused is opaque or translucent semi-crystalline.Therefore, optimum preparating condition is heating temperature
More than or equal to 175 DEG C, pumping rate is greater than 200MPa/min, and dwell pressure is greater than 250MPa.
The foregoing is only a preferred embodiment of the present invention, not does limitation in any form to the present invention, though
So present invention preferred embodiment is disclosed above, and however, it is not intended to limit the invention, any person skilled in the art,
Without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or are modified to
With the equivalent embodiment of variation, but without departing from the technical solutions of the present invention, according to the technical essence of the invention to above
Any simple modification, equivalent change and modification made by embodiment still belong within the scope of the technical scheme of the invention.
Claims (6)
1. a kind of method that pressurization prepares amorphous polylactic acid plate at a slow speed, by polylactic acid raw material heating melting, then with a constant speed
Degree is forced into dwell pressure, room temperature is down in pressure maintaining period, last release obtains amorphous polylactic acid plate, it is characterised in that: adds
Heat fusing temperature is 175 DEG C ~ 195 DEG C, pressing speed 200MPa/min-1000MPa/min, dwell pressure 250MPa-
1000MPa。
2. the method that pressurization at a slow speed according to claim 1 prepares amorphous polylactic acid plate, it is characterised in that: the pressurization
Speed is 300MPa/min-500MPa/min, dwell pressure 400MPa-500MPa.
3. the method that pressurization at a slow speed according to claim 1 prepares amorphous polylactic acid plate, it is characterised in that: the amorphous
Polylactic acid plate with a thickness of 1mm-10mm.
4. the method that pressurization at a slow speed according to claim 1 prepares amorphous polylactic acid plate, it is characterised in that: the release
In the process, release speed is less than 100MPa/min.
5. the method that pressurization at a slow speed according to claim 1 prepares amorphous polylactic acid plate, it is characterised in that: polylactic acid is former
Material first carries out vacuum drying pretreatment before the heating melting.
6. the method that pressurization at a slow speed according to claim 1 prepares amorphous polylactic acid plate, it is characterised in that: the poly- cream
Acid starting material is Poly L-lactic acid, poly- L-lactic acid or Poly L-lactic acid and the mixture that poly- L-lactic acid arbitrary proportion mixes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810137180.6A CN108340529B (en) | 2018-02-10 | 2018-02-10 | A method of pressurization prepares amorphous polylactic acid plate at a slow speed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810137180.6A CN108340529B (en) | 2018-02-10 | 2018-02-10 | A method of pressurization prepares amorphous polylactic acid plate at a slow speed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108340529A CN108340529A (en) | 2018-07-31 |
| CN108340529B true CN108340529B (en) | 2019-11-05 |
Family
ID=62959264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810137180.6A Active CN108340529B (en) | 2018-02-10 | 2018-02-10 | A method of pressurization prepares amorphous polylactic acid plate at a slow speed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108340529B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939691A (en) * | 2006-09-11 | 2007-04-04 | 东华大学 | Micro-structure formation of polylactic acid/epsilon-polycaprolester block copolymer |
| CN102941640A (en) * | 2012-10-09 | 2013-02-27 | 四川大学 | High pressure forming method for increasing crystallinity of polylactic acid |
| CN104788921A (en) * | 2015-04-07 | 2015-07-22 | 四川大学 | Transparent sc-PLA (stereocomplex polylactic acid) product with high degree of crystallinity and preparation method of transparent sc-PLA product |
| CN106393660A (en) * | 2016-08-31 | 2017-02-15 | 苏州西脉新诚生物科技有限公司 | Preparation method for oriented-state polylactic acid section bar |
| CN106426973A (en) * | 2016-08-31 | 2017-02-22 | 苏州西脉新诚生物科技有限公司 | Method for preparing orientated-state polylactic acid profile |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3687354B2 (en) * | 1998-06-30 | 2005-08-24 | トヨタ自動車株式会社 | Polylactic acid stereocomplex polymer composition |
-
2018
- 2018-02-10 CN CN201810137180.6A patent/CN108340529B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939691A (en) * | 2006-09-11 | 2007-04-04 | 东华大学 | Micro-structure formation of polylactic acid/epsilon-polycaprolester block copolymer |
| CN102941640A (en) * | 2012-10-09 | 2013-02-27 | 四川大学 | High pressure forming method for increasing crystallinity of polylactic acid |
| CN104788921A (en) * | 2015-04-07 | 2015-07-22 | 四川大学 | Transparent sc-PLA (stereocomplex polylactic acid) product with high degree of crystallinity and preparation method of transparent sc-PLA product |
| CN106393660A (en) * | 2016-08-31 | 2017-02-15 | 苏州西脉新诚生物科技有限公司 | Preparation method for oriented-state polylactic acid section bar |
| CN106426973A (en) * | 2016-08-31 | 2017-02-22 | 苏州西脉新诚生物科技有限公司 | Method for preparing orientated-state polylactic acid profile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108340529A (en) | 2018-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102241830B (en) | Preparation method of biodegradable polymer foamed sheet product | |
| Madbouly et al. | Biodegradation behavior of bacterial-based polyhydroxyalkanoate (PHA) and DDGS composites | |
| CN102532837B (en) | Preparation method for high molecular weight polylactic acid steric composite | |
| Yin et al. | Effect of plasticizer on the morphology and foaming properties of poly (vinyl alcohol) foams by supercritical CO 2 foaming agents | |
| CN105131538B (en) | A kind of PET foaming products and preparation method thereof | |
| Rezaei et al. | The effect of diameter on the thermal properties of the modeled shape-stabilized phase change nanofibers (PCNs) | |
| Kim et al. | Unique crystallization behavior of multi-walled carbon nanotube filled poly (lactic acid) | |
| Xia et al. | Effects of chain extender and uniaxial stretching on the properties of PLA/PPC/mica composites | |
| CN104530665B (en) | A kind of inexpensive industrial production process for the high-strength temperature-resistant PLA product that simplicity is controllable | |
| CN108587090B (en) | Biodegradable antistatic polylactic acid non-woven fabrics slice of one kind and preparation method thereof | |
| Grande et al. | Ternary melt blends of poly (lactic acid)/poly (vinyl alcohol)-chitosan | |
| Běhálek et al. | Study of crystallization of polylactic acid composites and nanocomposites with natural fibres by DSC method | |
| CN108340529B (en) | A method of pressurization prepares amorphous polylactic acid plate at a slow speed | |
| CN102584567B (en) | Efficient polylactic acid nucleating agent, and preparation method and application thereof | |
| CN103819690B (en) | Degraded null method prepares the technique of high-crystallinity poly(lactic acid) | |
| Maiti et al. | Structural changes of starch/polyvinyl alcohol biocomposite films reinforced with microcrystalline cellulose due to biodegradation in simulated aerobic compost environment | |
| Zou et al. | Self-nucleation efficiency of PDLA in PLAs: crystallization behavior and morphology | |
| Mohamed | The effect of annealing treatments on spherulitic morphology and physical ageing on glass transition of poly lactic acid (PLLA) | |
| Barman et al. | Mechanical properties of melt-spun monofilaments produced from virgin and recycled poly (ethylene terephthalate) blends | |
| Kawahara et al. | Direct resinification of two (1→ 3)-β-D-glucans, curdlan and paramylon, via hot-press compression molding | |
| CN108752956B (en) | Preparation method and application of polylactic acid crystallization nucleating agent and material based on humic acid | |
| Han et al. | Corn straw@ polypyrrole supported eutectic mixture aerogels for high-performance phase change composites | |
| CN105621400A (en) | Method for preparing graphene by using carbonate as raw material | |
| CN105968559B (en) | The preparation method of crystal type thermoplastic resin based composite material | |
| CN107474495A (en) | Modified PBAT resin combination and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |