CN101050301A - Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana - Google Patents
Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana Download PDFInfo
- Publication number
- CN101050301A CN101050301A CNA2007100722243A CN200710072224A CN101050301A CN 101050301 A CN101050301 A CN 101050301A CN A2007100722243 A CNA2007100722243 A CN A2007100722243A CN 200710072224 A CN200710072224 A CN 200710072224A CN 101050301 A CN101050301 A CN 101050301A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- lanthana
- composite material
- nano composite
- 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.)
- Granted
Links
Images
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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
This invention discloses a method for preparing plasticized poly (lactic acid)/lanthanum oxide modified montmorillonite nanocomposite. The method solves the problems of complex process, low compatibility between montmorillonite and poly (lactic acid), low flexibility and uneasy industrialization faced by the present technique. The method comprises: vacuum-drying poly (lactic acid) granules, nanoscale montmorillonite and lanthanum oxide, mixing lanthanum oxide and nanoscale montmorillonite to obtain lanthanum oxide-modified nanoscale montmorillonite, mixing poly (lactic acid) granules, lanthanum oxide-modified nanoscale montmorillonite and plasticizer, and extruding by a screw extruder to obtain plasticized poly (lactic acid)/lanthanum oxide modified montmorillonite nanocomposite. The method is simple and suitable for industrialization, and can improve the compatibility between montmorillonite and poly (lactic acid) matrix, and the flexibility of poly (lactic acid) material (elongation at break = 213%).
Description
Technical field
The present invention relates to a kind of preparation method of macromolecular material, be specifically related to the preparation method of poly lactic acid nano composite material.
Background technology
Poly(lactic acid) (PLA) is a kind of macromolecular material, and it is the polymkeric substance that dehydrating condensation forms between lactic acid molecules.The raw materials for production of poly(lactic acid) are reproducible farm crop, and this makes poly(lactic acid) have excellent biocompatibility and biodegradability.It is acknowledged as the material of green non-pollution, also is one of macromolecular material of at present tool development prospect, now has been widely used in fields such as medical science and wrapping material.
But simple poly-lactic acid material character is crisp, intensity is little, snappiness is poor, poor heat stability, and these deficiencies have restricted poly(lactic acid) and used widely.The appearance of these problems makes that people begin the modification of poly-lactic acid material is studied, to improve the performances such as intensity, snappiness and thermostability of poly(lactic acid).At present, the method that poly(lactic acid) is carried out modification mainly is to wherein adding inorganic fillers, adds that the partial properties of poly(lactic acid) increases behind the filler.Inorganic fillers mainly contains polynite, mica, talcum etc.Polynite is a kind of natural mineral matter, is acknowledged as present optimal filler because of abundant, the easy acquisition in its source, low price and modification performance are good.Nano-composite material of poly lactic acid/montmorillonite also has good performance because of it, and becomes the emphasis of current polylactic acid modified research.
The method for preparing Nano-composite material of poly lactic acid/montmorillonite mainly contains two kinds: solution intercalation method and melt intercalated method.Solution intercalation method long reaction time, and the organic solvent that will use in the preparation process work the mischief to human body as meetings such as chloroforms, and environment is polluted, and are unfavorable for suitability for industrialized production.
At present, the Nano-composite material of poly lactic acid/montmorillonite for preparing with the fusion intercalation method, all belong to part intercalation exfoliated nano-composite mostly, the original crystalline structure of polynite still exists, the mechanical strength of Nano-composite material of poly lactic acid/montmorillonite is necessarily improved, and its flexible increasing substantially is also rarely had report.A kind of method for preparing Nano-composite material of poly lactic acid/montmorillonite is provided among the patent CN 1760265A, and this method prepares masterbatch with the method for melt blending earlier, then masterbatch again with the matrix melt blending.Though its intensity of Nano-composite material of poly lactic acid/montmorillonite and the thermostability that obtain by this method increase, for reflecting that the flexible elongation at break of material is not described in detail; Though this method expands the interlamellar spacing of polynite to 3-5nm by 1-2nm, but still belong to intercalation type nano composite material.And through twice fusion intercalation, make process complications, be unsuitable for suitability for industrialized production.
Summary of the invention
The objective of the invention is to exist complex process, polynite and poly(lactic acid) consistency low, little and be unsuitable for the problem of suitability for industrialized production, a kind of preparation method of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana is provided the snappiness raising of material in order to solve the existing method that prepare Nano-composite material of poly lactic acid/montmorillonite.The preparation method's of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana of the present invention step is as follows: (one) pulverizes the back with poly(lactic acid) and crosses 40 mesh sieves, obtains the poly(lactic acid) particle; (2) with poly(lactic acid) particle, nano imvite and lanthanum trioxide 65～75 ℃ of following vacuum-dryings 3～5 hours; (3) with dried nano imvite and lanthanum trioxide by 40～60: 1 mass ratio mixes 5～15min in 65～75 ℃, the high-speed mixer of 800rpm, obtain the lanthana modification polynite; (4) poly(lactic acid) particle, lanthana modification polynite and softening agent are mixed 5～15min in 55～65 ℃, the high-speed mixer of 800rpm, wherein the weight percent of each component is: poly(lactic acid) particle 75～85%, lanthana modification polynite 0.5～5%, softening agent 10～20%; (5) mixture that obtains in the step (four) is joined in the screw extrusion press, temperature is that 140～170 ℃, screw speed are 10～15rpm, obtains Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana after extruding.
The present invention has reduced the agglomeration of nano imvite particle by with lanthanum trioxide nano imvite being carried out modification, and by fusion intercalation nano imvite is peeled off fully, has improved the consistency of nano imvite and poly(lactic acid) matrix.The lanthana modification polynite can improve the tensile strength and the flexural strength of poly(lactic acid), and softening agent can improve the elongation at break of poly(lactic acid).Lanthana modification polynite and softening agent are collaborative to polylactic acid modified, in the mechanical strength and thermostability that guarantee poly(lactic acid), have increased the snappiness of poly(lactic acid), and its elongation at break maximum can reach 213%.The present invention has only carried out fusion intercalation one time, compares with the method for twice fusion intercalation, has simplified technology, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 carries out the electron-microscope scanning figure of the surface of fracture after the tension test for simple poly-lactic acid material; Fig. 2 is the electron-microscope scanning figure that the Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana to embodiment 13 preparation carries out the surface of fracture after the tension test; Fig. 3 is the transmission electron microscope picture of the dispersing morphology of lanthana modification polynite in the poly(lactic acid) matrix in the embodiment 13; The X-ray diffraction spectrogram of moulding poly(lactic acid)/lanthana modification Nano composite material of montmorillonite that Fig. 4 prepares for the lanthana modification polynite in the embodiment 13 and this mode.
Embodiment
Embodiment one: the preparation method's of present embodiment Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana step is as follows: (one) pulverizes the back with poly(lactic acid) and crosses 40 mesh sieves, obtains the poly(lactic acid) particle; (2) with poly(lactic acid) particle, nano imvite and lanthanum trioxide 65～75 ℃ of following vacuum-dryings 3～5 hours; (3) with dried nano imvite and lanthanum trioxide by 40～60: 1 mass ratio mixes 5～15min in 65～75 ℃, the high-speed mixer of 800rpm, obtain the lanthana modification polynite; (4) poly(lactic acid) particle, lanthana modification polynite and softening agent are mixed 5～15min in 55～65 ℃, the high-speed mixer of 800rpm, wherein the weight percent of each component is: poly(lactic acid) particle 75～85%, lanthana modification polynite 0.5～5%, softening agent 10～20%; (5) mixture that obtains in the step (four) is joined in the screw extrusion press, temperature is that 140～170 ℃, screw speed are 10～15rpm, obtains Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana after extruding.
Embodiment two: the difference of present embodiment and embodiment one is: in the step (two) with poly(lactic acid) particle, nano imvite and lanthanum trioxide 70 ℃ of following vacuum-dryings 4 hours.Other is identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 41～59: 1 in the step (three).Other is identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 42～58: 1 in the step (three).Other is identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 43～57: 1 in the step (three).Other is identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 45～55: 1 in the step (three).Other is identical with embodiment one.
Embodiment seven: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 47～53: 1 in the step (three).Other is identical with embodiment one.
Embodiment eight: the difference of present embodiment and embodiment one is: the mass ratio of nano imvite and lanthanum trioxide is 50: 1 in the step (three).Other is identical with embodiment one.
Embodiment nine: present embodiment with the difference of embodiment one is: in the step (three) dried nano imvite and lanthanum trioxide are mixed 10min in 70 ℃, the high-speed mixer of 800rpm.Other is identical with embodiment one.
Embodiment ten: the difference of present embodiment and embodiment one is: softening agent is polyoxyethylene glycol or butylene sebacate in the step (four).Other is identical with embodiment one.
Embodiment 11: the difference of present embodiment and embodiment one is: the weight percent of each component is in the step (four): poly(lactic acid) particle 77～84%, lanthana modification polynite 1～4%, softening agent 12～19%.Other is identical with embodiment one.
Embodiment 12: the difference of present embodiment and embodiment one is: the weight percent of each component is in the step (four): poly(lactic acid) particle 80～83%, lanthana modification polynite 2～3%, softening agent 14～18%.Other is identical with embodiment one.
Embodiment 13: the difference of present embodiment and embodiment one is: the weight percent of each component is in the step (four): poly(lactic acid) particle 82.3%, lanthana modification polynite 1%, softening agent 16.7%.Other is identical with embodiment one.
As seen from Figure 1, the section of simple poly-lactic acid material is smooth, does not have tangible tensile yield phenomenon, shows as the feature of typical polymkeric substance brittle rupture; As seen from Figure 2, the section of the Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana of present embodiment preparation shows typical ductile rupture, fracture surface is very fuzzy and a large amount of fibrous plastic deformations are arranged, absorbed a large amount of ballistic works, illustrative material have a very strong snappiness.Table 1 is the related data of this test.As can be seen from Table 1, the mechanical strength of the Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana of present embodiment preparation remains unchanged substantially, and the elongation at break raising reaches 213.51%.
Table 1
| Example | Tensile strength (MPa) | Elongation at break (%) | Second-order transition temperature (℃) | Fusing point (℃) | Degree of crystallinity (%) |
| Simple poly-lactic acid material | 55.48 | 0 | 60.4 | 150.7 | 6.9 |
| Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana | 46.82 | 213.51 | 58.2 | 147.0 | 26.4 |
As seen from Figure 3, the lamella ordered structure of nano imvite is broken fully in the poly(lactic acid) matrix, and the nano imvite particle is not reunited together, and most forms of peeling off with monolithic are dispersed in the poly(lactic acid) matrix.Among Fig. 4, curve 1 and curve 2 are respectively the X-ray diffraction curve of lanthana modification polynite and Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana.The multilayer of nano imvite crystal grain periodically ordered structure characterizes with the X-ray diffraction spectrogram.According to the Bragg equation: 2dsin θ=n λ, can calculate interlamellar spacing d, θ is the feature angle of diffraction of lanthana modification polynite in the present embodiment in the formula, and λ is the wavelength of X ray, and n is a diffraction progression.According to angle of diffraction that records the lanthana modification polynite in the X-ray diffraction and Bragg equation, calculate the interlamellar spacing d=2.4nm of lanthana modification polynite.The characteristic diffraction peak of lanthana modification polynite does not appear in the Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana of embodiment 13 preparations in the corresponding position of the characteristic diffraction peak of lanthana modification polynite, and the diffraction curve in corresponding angle of diffraction scope is a smooth curve, illustrate that nano imvite peels off fully, the nano imvite particle with bigger size dispersion in the poly(lactic acid) matrix, the consistency of nano imvite and poly(lactic acid) matrix.
Embodiment 14: the difference of present embodiment and embodiment one is: the mixture in the step (five) joins in the screw extrusion press, and temperature is 150～160 ℃, and screw speed is 12rpm.Other is identical with embodiment one.
Claims (10)
1, a kind of preparation method of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana, preparation method's the step that it is characterized in that Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana is as follows: (one) pulverizes the back with poly(lactic acid) and crosses 40 mesh sieves, obtains the poly(lactic acid) particle; (2) with poly(lactic acid) particle, nano imvite and lanthanum trioxide 65～75 ℃ of following vacuum-dryings 3～5 hours; (3) with dried nano imvite and lanthanum trioxide by 40～60: 1 mass ratio mixes 5～15min in 65～75 ℃, the high-speed mixer of 800rpm, obtain the lanthana modification polynite; (4) poly(lactic acid) particle, lanthana modification polynite and softening agent are mixed 5～15min in 55～65 ℃, the high-speed mixer of 800rpm, wherein the weight percent of each component is: poly(lactic acid) particle 75～85%, lanthana modification polynite 0.5～5%, softening agent 10～20%; (5) mixture that obtains in the step (four) is joined in the screw extrusion press, temperature is that 140～170 ℃, screw speed are 10～15rpm, obtains Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana after extruding.
2, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that in the step (two) poly(lactic acid) particle, nano imvite and lanthanum trioxide 70 ℃ of following vacuum-dryings 4 hours.
3, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that the mass ratio of middle nano imvite of step (three) and lanthanum trioxide is 42～58: 1.
4, a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana preparation method according to claim 1 is characterized in that the mass ratio of middle nano imvite of step (three) and lanthanum trioxide is 50: 1.
5, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that in the step (three) dried nano imvite and lanthanum trioxide are mixed 10min in 70 ℃, the high-speed mixer of 800rpm.
6, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that softening agent is polyoxyethylene glycol or butylene sebacate in the step (four).
7, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that the weight percent of each component in the step (four) is: poly(lactic acid) particle 77～84%, lanthana modification polynite 1～4%, softening agent 12～19%.
8, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that the weight percent of each component in the step (four) is: poly(lactic acid) particle 80～83%, lanthana modification polynite 2～3%, softening agent 14～18%.
9, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1 is characterized in that the weight percent of each component in the step (four) is: poly(lactic acid) particle 82.3%, lanthana modification polynite 1%, softening agent 16.7%.
10, the preparation method of a kind of Nano composite material of montmorillonite modified by plasticized poly lactic acid/lanthana according to claim 1, it is characterized in that the mixture in the step (five) joins in the screw extrusion press, temperature is that 150～160 ℃, screw speed are 12rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100722243A CN100415829C (en) | 2007-05-18 | 2007-05-18 | Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100722243A CN100415829C (en) | 2007-05-18 | 2007-05-18 | Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101050301A true CN101050301A (en) | 2007-10-10 |
| CN100415829C CN100415829C (en) | 2008-09-03 |
Family
ID=38781913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100722243A Expired - Fee Related CN100415829C (en) | 2007-05-18 | 2007-05-18 | Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415829C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875765A (en) * | 2010-07-14 | 2010-11-03 | 华东理工大学 | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof |
| CN101328308B (en) * | 2008-07-29 | 2011-05-11 | 武汉理工大学 | High tenacity biodegradable polylactic acid film and preparation thereof |
| CN103041789A (en) * | 2012-12-26 | 2013-04-17 | 青岛佰众化工技术有限公司 | Polylactic acid/palygorskite/polyethylene glycol absorption film |
| CN107778463A (en) * | 2017-12-05 | 2018-03-09 | 桐乡守敬应用技术研究院有限公司 | A kind of nano montmorillonite modified PLA |
| CN108752632A (en) * | 2018-06-20 | 2018-11-06 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of the quaternary ammonium salt-modified nanometer organic montmorillonite of easily disperse |
| CN113373521A (en) * | 2020-01-19 | 2021-09-10 | 包头稀土研究院 | Lanthanum hydroxide nano whisker and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338796A (en) * | 2001-05-21 | 2002-11-27 | Teijin Ltd | Biodegradable gas-barrier material |
| JP4982934B2 (en) * | 2001-09-05 | 2012-07-25 | 株式会社豊田中央研究所 | Biodegradable resin composite material |
| CN1760265A (en) * | 2005-10-13 | 2006-04-19 | 同济大学 | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite |
-
2007
- 2007-05-18 CN CNB2007100722243A patent/CN100415829C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328308B (en) * | 2008-07-29 | 2011-05-11 | 武汉理工大学 | High tenacity biodegradable polylactic acid film and preparation thereof |
| CN101875765A (en) * | 2010-07-14 | 2010-11-03 | 华东理工大学 | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof |
| CN103041789A (en) * | 2012-12-26 | 2013-04-17 | 青岛佰众化工技术有限公司 | Polylactic acid/palygorskite/polyethylene glycol absorption film |
| CN107778463A (en) * | 2017-12-05 | 2018-03-09 | 桐乡守敬应用技术研究院有限公司 | A kind of nano montmorillonite modified PLA |
| CN108752632A (en) * | 2018-06-20 | 2018-11-06 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of the quaternary ammonium salt-modified nanometer organic montmorillonite of easily disperse |
| CN113373521A (en) * | 2020-01-19 | 2021-09-10 | 包头稀土研究院 | Lanthanum hydroxide nano whisker and preparation method and application thereof |
| CN113373521B (en) * | 2020-01-19 | 2024-03-29 | 包头稀土研究院 | Lanthanum hydroxide nanowhisker and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100415829C (en) | 2008-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100415829C (en) | Method for preparing Nano composite material of montmorillonite modified by plasticized poly lactic acid / lanthana | |
| Qian et al. | Effects of bamboo cellulose nanowhisker content on the morphology, crystallization, mechanical, and thermal properties of PLA matrix biocomposites | |
| Yang et al. | Sustainable packaging biocomposites from polylactic acid and wheat straw: Enhanced physical performance by solid state shear milling process | |
| Li et al. | Extensional flow-induced hybrid crystalline fibrils (shish) in CNT/PLA nanocomposite | |
| CN105200547A (en) | Preparation method of graphene-polyester nano-composite fiber | |
| JP6482543B2 (en) | Polymer resin composite containing biomass nanofiber, method for producing biomass nanofiber, and method for producing the same | |
| Huang et al. | Poly (vinyl alcohol)/artificial marble wastes composites with improved melt processability and mechanical properties | |
| CN108929527B (en) | PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof | |
| CN113248798B (en) | starch/cellulose/PBAT composite film and preparation method thereof | |
| Chang et al. | Ductile polyacrylonitrile fibers with high cellulose nanocrystals loading | |
| Li et al. | Flexible dielectric nanocomposite films based on chitin/boron nitride/copper calcium titanate with high energy density | |
| Wu et al. | Effect of elongational rheology on plasticization and properties of thermoplastic starch prepared by biaxial eccentric rotor extruder | |
| Tian et al. | Effect of microfibrillated cellulose loading on physical properties of starch/polyvinyl alcohol composite films | |
| CN101623516B (en) | In-situ fiber-forming strengthened degradable medical elastic composite material and preparation method thereof | |
| CN111087773A (en) | PLA/PBAT/nano SiO2Method for preparing composite material | |
| CN109853065A (en) | Graphene composite fibre and preparation method thereof | |
| CN112121650B (en) | Nano-fiber chitosan membrane and preparation method thereof | |
| KR102478218B1 (en) | Manufacturing method of composite by mixing cnf and biodegradable polymer to enhance the mechanical properties of biodegradable plastics | |
| CN106009559A (en) | Preparation method of high-strength and high-toughness PLA (polylactic acid) and in-situ nanofiber composite | |
| CN111978719A (en) | Polyamide 66 composite material and preparation method thereof | |
| CN110698832A (en) | Nano particle reinforced flame-retardant aging-resistant PC composite material and preparation method thereof | |
| CN117510928A (en) | Preparation method of high-toughness cellulose microgel/plasticized starch/PBAT (Poly-butylene terephthalate) film material | |
| CN117467286A (en) | Modified heavy calcium carbonate, preparation method and application thereof in producing degradable PBAT material | |
| Bommanna et al. | Influence of Twin-Screw Extrusion on The Dispersion of Nanoclay in Vinylester Composites | |
| CN116444967A (en) | PLA and PPC composite material with isolation structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080903 |