CN107216626B - A kind of preparation method of polycaprolactone and starch nano crystal composite material - Google Patents
A kind of preparation method of polycaprolactone and starch nano crystal composite material Download PDFInfo
- Publication number
- CN107216626B CN107216626B CN201710583952.4A CN201710583952A CN107216626B CN 107216626 B CN107216626 B CN 107216626B CN 201710583952 A CN201710583952 A CN 201710583952A CN 107216626 B CN107216626 B CN 107216626B
- Authority
- CN
- China
- Prior art keywords
- polycaprolactone
- composite material
- crystal
- nanometer starch
- starch crystal
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/30—Applications used for thermoforming
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
A kind of preparation method of polycaprolactone and starch nano crystal composite material, is related to the preparation technical field of polycaprolactone composite material., through drying, laminated film will be made, then through hot press molding, obtain polycaprolactone and starch nano crystal composite material after the alcohol dispersion liquid of nanometer starch crystal and polycaprolactone solution blending.Guarantee that nanometer starch crystal good dispersion, nanoparticle in polycaprolactone are uniformly dispersed in gained composite material of the invention, mechanical property, crystal property significantly improve.According to needs of production, the composite material of the available different-thickness of hot-forming pressure, mold is adjusted.
Description
Technical field
The present invention relates to the preparation technical fields of polycaprolactone composite material.
Background technique
Polycaprolactone is a kind of biodegradable semicrystalline polymeric, due to containing ester group on structural unit, so that
It is widely used in agricultural film, environment-friendly materials and medical field with excellent flexibility, processability and biocompatibility.
Polycaprolactone still has some shortcomings as the use aspect of packaging material for food or agricultural film material at present, such as strong
Degree, crystallinity, creep-resistant property are poor.Polycaprolactone is blended with other fillers and prepares composite material to be that one kind mentions high performance
Effective ways, it is multiple that a large amount of document report using nano silica, graphene oxide, carbon nanotube etc. prepares polycaprolactone
Condensation material, but these non-degradables, coloured filler limit the application field of polycaprolactone composite material.
Starch from nature is by handling available nanometer starch crystal, due to excellent mechanical performance, biology
Degradability and biocompatibility, nanometer starch crystal have obtained more and more extensive concern.CN201310264825.X,
The patent documents such as CN201310352678.1, CN201610162973.4 disclose the preparation method of nanometer starch crystal, with corn
Starch or rice starch are raw material, can obtain the particle that diameter is tens nanometer by sulphuric acid hydrolysis.Nanometer starch crystal is usually used in rubber
The enhancing of glue and plastics, studies have found that, the additive amount of nanometer starch crystal is only 5% or so, and the mechanical property of material can obtain
It is remarkably reinforced.Document report prepares nanometer starch crystal/polymer composites technique: nanometer starch crystal is prepared, it will
Nanometer starch crystal freeze-drying or spray drying, prepare composite material by melt blending.Since nanometer starch crystal surface is contained
More hydroxyl, traditional drying means will lead to it and irreversible reunion occur, and lose the dimensional effect of nanofiller, increase
Strong declines.Freeze-drying and spray drying technology usually can reduce the reunion of nanometer starch crystal, but cannot avoid completely
The reunion of nano particle, and process when this is a consumption energy consumption, it is multiple largely to constrain nanometer starch crystal/polymer
The industrialized production of condensation material.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of polycaprolactone and starch nano crystal composite material
Preparation method.
The technical scheme is that: by after the alcohol dispersion liquid of nanometer starch crystal and polycaprolactone solution blending through drying,
Laminated film is made, then through hot press molding, obtains polycaprolactone and starch nano crystal composite material.
The present invention prepares composite material by solution blending and hot-forming method.Guarantee starch in gained composite material
Nanocrystalline dispersion good in polycaprolactone, nanoparticle are uniformly dispersed, and mechanical property, crystal property significantly improve.According to
Needs of production adjusts the composite material of the available different-thickness of hot-forming pressure, mold.Present invention process path
Simply, composite property is excellent, can be applied to environment-friendly material and industrial product industry.
The method that the above acidolysis prepares nanometer starch crystal be in CN201310264825.X, CN201310352678.1,
It is realized on the basis of the patent documents such as CN201610162973.4.Neutral nanometer starch crystal is washed to be sufficiently mixed with ethyl alcohol,
Supernatant liquor is removed in centrifugation hypsokinesis.This process utilizes second alcohol and water intersolubility, and ethyl alcohol centrifuge washing is operated 3-4 times repeatedly, gradually removed
Water in the nanocrystalline dispersion liquid of desizing.Ultrasonic disperse after ethyl alcohol is added in last time sediment, obtains nanometer starch crystal ethyl alcohol point
Dispersion liquid.Under the action of ultrasound, nanometer starch crystal can be very good dispersion in ethanol, form stable dispersion liquid, in case after
Continuous step uses.Nanometer starch crystal is not necessarily to drying, it is entirely avoided the reunion in drying process.
In order to improve dispersibility of the nanometer starch crystal in polycaprolactone, the present invention by nanometer starch crystal alcohol dispersion liquid and
Polycaprolactone solution blending prepares laminated film.Disperse nanometer starch crystal in ethyl alcohol, after centrifugation taking precipitate again with second
Alcohol is sufficiently mixed, and is centrifuged taking precipitate, is operated 3~4 times repeatedly, is taken last time sediment that ultrasonic disperse after ethyl alcohol is added, is obtained
The alcohol dispersion liquid of nanometer starch crystal.To obtain optimal dispersion effect；Polycaprolactone is dissolved in solvent, forms stable homogeneous
Solution.Further, it by resulting nanometer starch crystal and polycaprolactone solution blending, volatilizees to obtain composite material by solvent.
Above-mentioned dispersion liquid and solution need to meet certain concentration range.Nanometer starch crystal in nanometer starch crystal alcohol dispersion liquid
Content be 0.01-0.12 g/ml, nanometer starch crystal content be greater than 0.12 g/ml when, stable dispersion liquid cannot be formed, form sediment
Powder is nanocrystalline to be present in alcohol dispersion liquid with biggish pulpous state aggregate, is unfavorable for subsequent mixing with polycaprolactone solution；Through
Overtesting, when nanometer starch crystal content is less than 0.12 g/ml, nanometer starch crystal can be evenly dispersed in ethyl alcohol.Starch is received
The brilliant content of rice is smaller, it is meant that the amount of required ethyl alcohol is bigger, causes a large amount of consumption of solvent.
Polycaprolactone dissolves in the one or more of chloroform, methylene chloride, acetone, above-mentioned single solvent or several molten
The compounding of agent is all the good solvent of polycaprolactone.The premise of solution blending is that polymer can be completely dissolved in solvent, strand energy
It is enough sufficiently to unfold；Meanwhile the viscosity of polycaprolactone solution is an important indicator, the viscosity of solution is lower be not easy to it is subsequent at
Film.Can the amount ranges of solvent be formed a film determination by observation polycaprolactone dissolution situation in a solvent and composite material, institute
The content for obtaining polycaprolactone in solution is 0.05-0.15 g/ml.
In order to form composite material, the alcohol dispersion liquid of the above nanometer starch crystal and feeding intake when polycaprolactone solution blending
Volume ratio is 1: 1.27~237.6.The design of the feed ratio is true according to the mass fraction of nanometer starch crystal in the composite
Fixed, the mass fraction of nanometer starch crystal is 1%~5wt%.The mass fraction of nanometer starch crystal and the performance of composite material are close
Connection can not form three-dimensional Percolation network, not be obviously improved work to the performance of material when its mass fraction is lower than 1wt%
With；When its mass fraction is higher than 5wt%, the extremely strong agglomeration of nanometer starch crystal itself plays negative growth to the performance of material
Effect.
Obtained polycaprolactone/nanometer starch crystal laminated film through hot pressing and is cooled to room temperature acquirement polycaprolactone/starch
Nanocrystalline composite material.Since the fusing point of polycaprolactone is generally 50~60 DEG C, the lowest temperature of hot pressing sets 60 DEG C；Due to it
Better heat stability does not degrade within 200 DEG C substantially, from the point of view of energy conservation, the hot pressing temperature upper limit is set
120℃。
Detailed description of the invention
Fig. 1 is each creep curve of 1 composite material of Examples 1 to 3 and comparative example.
Fig. 2 is the decrease temperature crystalline curve after Examples 1 to 3 and the melting of 1 composite material of comparative example.
Fig. 3 is 1 composite material tearing strength figure of Examples 1 to 3 and comparative example.
Specific embodiment
Other advantages of the invention and effect will continue to describe in the following detailed description.
Polycaprolactone solvent can be the one or more of chloroform, methylene chloride, acetone, and following table is different solvents pair
The solvent case of polycaprolactone.
1 different solvents of table are to the dissolution situation of polycaprolactone ("+" represent dissolubility is good, and it is bad that "-" represents dissolubility)
| Polycaprolactone solvent | Chloroform | Methylene chloride | Acetone | Chloroform, methylene chloride | Chloroform, acetone | Methylene chloride, acetone | Chloroform, methylene chloride, acetone |
| Dissolve situation | + | + | + | + | + | + | + |
Chloroform, methylene chloride, acetone any compounding of one or more be all the good solvent of polycaprolactone, Ke Yishi
The solution blending of existing polycaprolactone composite material.During laminated film dries and is subsequent hot-forming, solvent can be abundant
Volatilization, will not have an impact the performance of composite material.In the following Examples and Comparative Examples, the molten of polycaprolactone solution is prepared
Agent uses chloroform.
Using cornstarch as raw material, CN201310264825.X, CN201310352678.1, CN201610162973.4 etc.
Nanometer starch crystal is made in sulphuric acid hydrolysis disclosed in patent document.
One, embodiment 1:
Take nanometer starch crystal, through ethyl alcohol centrifuge washing taking precipitate, then plus ethyl alcohol centrifuge washing sediment operate 3 repeatedly~
It 4 times, takes last time sediment that ultrasonic disperse after ethyl alcohol is added, obtains the alcohol dispersion liquid of nanometer starch crystal, wherein starch nano
Brilliant content is 0.12 g/ml.
Prepare the chloroform soln for the polycaprolactone that content is 0.05 g/ml.
The alcohol dispersion liquid of 10 mL nanometer starch crystals is mixed with the chloroform soln of 2376 mL polycaprolactones, sufficiently
Stirring, after the solvent volatilization of body to be mixed, drying to constant weight, obtains polycaprolactone and nanometer starch crystal laminated film.
Through detecting, nanometer starch crystal quality accounting is 1wt% in laminated film.
Laminated film is hot-forming under the conditions of 120 DEG C, obtain the composite material of polycaprolactone and nanometer starch crystal.
Two, embodiment 2:
Take nanometer starch crystal, through ethyl alcohol centrifuge washing taking precipitate, then plus ethyl alcohol centrifuge washing sediment operate 3 repeatedly~
It 4 times, takes last time sediment that ultrasonic disperse after ethyl alcohol is added, obtains the alcohol dispersion liquid of nanometer starch crystal, wherein starch nano
Brilliant content is 0.1 g/ml.
Prepare the chloroform soln for the polycaprolactone that content is 0.1 g/ml.
The alcohol dispersion liquid of 3 mL nanometer starch crystals is mixed with the chloroform soln of 97 mL polycaprolactones, is sufficiently stirred
It mixes, after the solvent volatilization of body to be mixed, drying to constant weight, obtains polycaprolactone and nanometer starch crystal laminated film.
Through detecting, nanometer starch crystal quality accounting is 3wt% in laminated film.
Laminated film is hot-forming under the conditions of 80 DEG C, obtain the composite material of polycaprolactone and nanometer starch crystal.
Three, embodiment 3:
Take nanometer starch crystal, through ethyl alcohol centrifuge washing taking precipitate, then plus ethyl alcohol centrifuge washing sediment operate 3 repeatedly~
It 4 times, takes last time sediment that ultrasonic disperse after ethyl alcohol is added, obtains the alcohol dispersion liquid of nanometer starch crystal, wherein starch nano
Brilliant content is 0.01g/ml.
Prepare the chloroform soln for the polycaprolactone that content is 0.15 g/ml.
The alcohol dispersion liquid of 10 mL nanometer starch crystals is mixed with the chloroform soln of 12.7 mL polycaprolactones, sufficiently
Stirring, after the solvent volatilization of body to be mixed, drying to constant weight, obtains polycaprolactone and nanometer starch crystal laminated film.
Through detecting, nanometer starch crystal quality accounting is 5wt% in laminated film.
Laminated film is hot-forming under the conditions of 60 DEG C, obtain polycaprolactone and starch nano crystal composite material.
Four, comparative example 1:
Polycaprolactone is directly dissolved in chloroform, is sufficiently stirred, obtains polycaprolactone material after solvent volatilization.
Five, it analyzes:
Fig. 1 is 1 creep of composite materials curve of embodiment 1-3 and comparative example, and embodiment 1-3 is to be added to nanometer starch crystal
Polycaprolactone composite material.By comparison, it was found that the addition of nanometer starch crystal can largely reduce the compacted of polycaprolactone
Become strain level, that is to say, the creep-resistant property of composite material is remarkably reinforced.Strain level is with nanometer starch crystal mass fraction
Increase and reduce, this is because caused by nanometer starch crystal hinders the movement of polycaprolactone strand.
Fig. 2 is the decrease temperature crystalline curve after embodiment 1-3 and the melting of 1 composite material of comparative example.It is tied in decrease temperature crystalline curve
The peak temperature at brilliant peak is often referred to as " crystallization temperature ", the addition of nanometer starch crystal, so that the crystallization temperature of polycaprolactone improves,
Illustrate that the addition of nanometer starch crystal plays the role of heterogeneous nucleation to the crystallization of polycaprolactone, promotes the knot of polycaprolactone
It is brilliant.For industrial production, faster crystalline rate can increase substantially production efficiency, and the addition of filler promotes crystallization may
The crystal structure that polycaprolactone can further be improved, promotes the performance of product.
Fig. 3 is 1 composite material tearing strength figure of embodiment 1-3 and comparative example, and the value of tearing strength is reflected as packaging
Tear resistance in material or agricultural film use process.With the increase of nanometer starch crystal mass fraction, tearing strength is in
Downward trend after now first rising.Nanometer starch crystal plays the role of similar bridge in the composite, composite material by
When to external force, the tearing strength of the effect promoting material of nanometer starch crystal connection molecule chain.
Claims (4)
1. the preparation method of a kind of polycaprolactone and starch nano crystal composite material, it is characterised in that: by the nanometer starch crystal
It being sufficiently mixed with ethyl alcohol, taking precipitate is sufficiently mixed with ethyl alcohol again after centrifugation, is centrifuged taking precipitate, it operates 3~4 times repeatedly,
It takes last time sediment that ultrasonic disperse after ethyl alcohol is added, obtains the alcohol dispersion liquid of nanometer starch crystal；By the second of nanometer starch crystal
Through drying after alcohol dispersion liquid and polycaprolactone solution blending, laminated film is made, then through hot press molding, obtains polycaprolactone and shallow lake
Powder nanocrystalline composite material.
2. the preparation method of composite material according to claim 1, it is characterised in that: the nanometer starch crystal of blending
The content of nanometer starch crystal is 0.01~0.12 g/ml in alcohol dispersion liquid；Gather in oneself in the polycaprolactone solution being blended
The content of ester is 0.05~0.15 g/ml, alcohol dispersion liquid and the body that feeds intake when polycaprolactone solution blending of nanometer starch crystal
Product is than being 1: 1.27~237.6.
3. the preparation method of composite material according to claim 1 or claim 2, it is characterised in that: molten in the polycaprolactone solution
Agent be chloroform, methylene chloride or acetone at least any one.
4. the preparation method of composite material according to claim 1, it is characterised in that: the temperature condition of the hot pressing be 60~
120℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710583952.4A CN107216626B (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of polycaprolactone and starch nano crystal composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710583952.4A CN107216626B (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of polycaprolactone and starch nano crystal composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107216626A CN107216626A (en) | 2017-09-29 |
| CN107216626B true CN107216626B (en) | 2019-06-21 |
Family
ID=59953265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710583952.4A Active CN107216626B (en) | 2017-07-18 | 2017-07-18 | A kind of preparation method of polycaprolactone and starch nano crystal composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107216626B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305568A (en) * | 2013-06-28 | 2013-09-18 | 江南大学 | Preparation method of starch nanocrystal ester |
| CN103602046A (en) * | 2013-11-18 | 2014-02-26 | 中国科学院化学研究所 | Biodegradable polyester nanocomposite material containing functionalized starch nanocrystal and preparation method of biodegradable polyester nanocomposite material |
| CN104844718A (en) * | 2015-05-18 | 2015-08-19 | 吉林大学 | Preparation method with high yield and short complexing time for starch nanocrystal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10246523B2 (en) * | 2015-08-04 | 2019-04-02 | Jiangnan University | Fluorescent starch nanocrystal and preparation method and application thereof |
-
2017
- 2017-07-18 CN CN201710583952.4A patent/CN107216626B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305568A (en) * | 2013-06-28 | 2013-09-18 | 江南大学 | Preparation method of starch nanocrystal ester |
| CN103602046A (en) * | 2013-11-18 | 2014-02-26 | 中国科学院化学研究所 | Biodegradable polyester nanocomposite material containing functionalized starch nanocrystal and preparation method of biodegradable polyester nanocomposite material |
| CN104844718A (en) * | 2015-05-18 | 2015-08-19 | 吉林大学 | Preparation method with high yield and short complexing time for starch nanocrystal |
Non-Patent Citations (1)
| Title |
|---|
| Structure and Mechanical Properties of Poly(lacticacid) Filled with (Starchnanocrystal)-graft-poly(e-caprolactone);Jiahui Yu et al.;《Macromol.Mater.Eng.》;20081231;第293卷(第9期);第763-770页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107216626A (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Comparative study on the films of poly (vinyl alcohol)/pea starch nanocrystals and poly (vinyl alcohol)/native pea starch | |
| CN105315508B (en) | A kind of preparation method of modified graphene chitosan laminated film | |
| CN105315507B (en) | A kind of method for preparing modified graphene chitosan laminated film | |
| CN103421286A (en) | High temperature resistant and degradable polylactic acid wood plastic material and preparation method thereof | |
| CN104087027B (en) | A kind of heat resist modification calcium carbonate and preparation method thereof | |
| CN102675804A (en) | Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof | |
| CN102295827A (en) | Method for preparing fully biodegradable nano-composite polyester plastic | |
| CN101875765A (en) | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof | |
| CN103992518B (en) | Biodegradable packaging material | |
| CN109825045A (en) | A kind of graphene composite biomass enhancing PBS/PBAT biological degradable composite material and preparation method thereof | |
| CN113604018A (en) | Polylactic acid-based nanocomposite material for 3D printing and preparation method thereof | |
| CN113788991A (en) | Biodegradable high-performance modified particle material and preparation method thereof | |
| CN106008931B (en) | A kind of PBS/ alkali magnesium sulfate crystal whiskers composite and preparation method | |
| CN111057289A (en) | LDPE/corn starch/TiO2Antibacterial composite membrane and preparation method thereof | |
| CN104163943B (en) | Thermoplastic cellulose composite material and preparation method thereof | |
| CN110343293A (en) | A kind of cellulose nano-fibrous/dopamine redox graphene enhancing starch film and preparation method thereof | |
| CN104893207A (en) | Polyvinyl alcohol/corn starch composite fully-degradable plastic film and preparation method thereof | |
| CN107216626B (en) | A kind of preparation method of polycaprolactone and starch nano crystal composite material | |
| CN103408927A (en) | Composite fiber modified nylon material and preparation method thereof | |
| CN104059391A (en) | Surface-treated modified calcium carbonate and preparation method thereof | |
| Ali et al. | Mechanical characterization and morphology of polylactic acid/liquid natural rubber filled with multi walled carbon nanotubes | |
| CN107964127A (en) | Modified thermoplastic starch of one metal ion species enhancing and its preparation method and application | |
| CN101012335A (en) | Nano composite soybean protein plastic and preparing method thereof | |
| CN102838880A (en) | Method for producing an environmentally-friendly type wood-plastic composite material by utilizing renewable resources | |
| CN103224653B (en) | A kind of Biodegradable nylon 6/ starch composite material 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 |