CN108752888B - Heat-resistant polylactic acid composition and preparation method thereof - Google Patents
Heat-resistant polylactic acid composition and preparation method thereof Download PDFInfo
- Publication number
- CN108752888B CN108752888B CN201810707445.1A CN201810707445A CN108752888B CN 108752888 B CN108752888 B CN 108752888B CN 201810707445 A CN201810707445 A CN 201810707445A CN 108752888 B CN108752888 B CN 108752888B
- Authority
- CN
- China
- Prior art keywords
- starch
- polylactic acid
- compound
- heat
- nucleating agent
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a heat-resistant polylactic acid composition and a preparation method thereof, belonging to the technical field of high polymer materials. The composition consists of polylactic resin and a starch compound, wherein the weight ratio of the starch compound to the polylactic resin is 1: 99-50: 50. The starch composite comprises a starch graft copolymer and a nucleating agent; the weight ratio of the starch graft copolymer to the nucleating agent is 100 (1-100). The polylactic acid composition is prepared by mixing the raw materials in a series and melting and blending. The invention has the advantages of environmental protection, low cost and simple process, and the degradable polylactic acid-based composition with controllable performance is obtained.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a heat-resistant polylactic acid composition and a preparation method thereof.
Background
In recent years, biodegradable materials have received high attention due to environmental problems. Polylactic acid (PLA) is a linear aliphatic thermoplastic polyester that can be fermented from renewable resources such as corn. Polylactic acid has been widely studied due to its good strength, rigidity, biodegradability and processability, but its application in more fields is limited by its low toughness and low heat distortion temperature. Currently, major factors that restrict PLA use and development include: slow crystallization rate, low crystallinity, low heat distortion temperature, high brittleness, relatively high cost, etc. It is an economical and effective method to improve the toughness of PLA by blending a flexible polymer such as PU, PE, EGMA, TPO, EVA, POE, PCL, PBAT, PHA, PBS, and PBSA with polylactic acid. However, these polymers have the problem of being non-biodegradable or costly and, after addition, significantly reduce the strength of the PLA. In addition, due to the slow crystallization rate of the material, the PLA articles produced in practice (e.g., injection molding) are generally amorphous, and when used at a glass transition temperature above 56 ℃, the mechanical strength and stiffness of the material will be significantly reduced. The slow crystallization rate of PLA is mainly due to the short lactic acid repeating unit in the molecular chain, the high rigidity of the main chain and the low motion capability of the molecular chain.
The addition of the nucleating agent can obviously improve the nucleation density of the PLA, thereby improving the crystallinity of the material. The addition of a nucleating agent can lower the surface free energy barrier required for PLA nucleation, so that the PLA melt begins to crystallize at a higher temperature. At present, the common nucleating agents for polylactic acid mainly comprise inorganic nucleating agents, organic nucleating agents and high-molecular nucleating agents.
Starch is an abundant, renewable and biodegradable carbohydrate polymer available at low cost from a variety of agricultural crops. As a polyhydroxy natural polymer, starch molecules are rigid and difficult to thermoplastically process. At the same time, the compatibility between PLA and starch is poor, since PLA is hydrophobic and starch is hydrophilic, and this incompatibility ultimately leads to poor blend properties. The starch graft copolymer can be processed by hot molding, and has the advantages of low cost, good hydrophobicity and good degradation performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polylactic acid composition and a preparation method thereof. The composition has the advantages of good compatibility among all components, good toughness, high heat distortion temperature, low cost, simple process and controllable performance, and is suitable for preparing thermoplastic materials with various performance requirements.
The technical scheme of the invention is as follows:
a heat resistant polylactic acid composition, the composition comprising the following components: polylactic resin and starch composites; the weight ratio of the starch compound to the polylactic resin is 1: 99-50: 50.
Further, the weight ratio of the starch compound to the polylactic resin is 2: 98-40: 60.
The starch composite comprises a starch graft copolymer and a nucleating agent; the weight ratio of the starch graft copolymer to the nucleating agent is 100 (1-100).
Furthermore, the weight ratio of the starch graft copolymer to the nucleating agent in the starch compound is 100 (1-60).
The nucleating agent is at least one of an organic nucleating agent and an organic modified inorganic nucleating agent.
The heat-resistant polylactic acid composition is characterized in that the organic nucleating agent is an amide compound, a hydrazide compound, a metal phosphate compound, an organic carboxylic acid and a derivative compound thereof; the organic modified inorganic nucleating agent is modified talcum powder, montmorillonite, halloysite or attapulgite.
The heat-resistant polylactic acid composition is characterized in that the amide compound is Ethylene Bis Stearamide (EBS), TMC-328 or CZ500 and the like; the hydrazide compound is TMC-300, CHC-300, TMC-306 and the like; the metal phosphate compounds are phenyl zinc phosphonate (TMC-200), Sanulant TMHK162, Sanulant TMHK160 and the like; the organic carboxylic acid and derivatives thereof are 2-chlorobenzoic acid sodium salt, tert-butyl benzoic acid aluminum, bis (p-tert-butyl benzoic acid) hydroxy aluminum (Al-PTBBA), beta-sodium naphthoate and the like.
The starch graft copolymer is prepared by copolymerizing starch treated by a modifier and a graft monomer. The weight ratio of the modifier to the starch is 1: 100-1: 10, and the weight ratio of the modified starch to the grafting monomer is 1: 1-1: 5.
The modifier is one or more than two of double-bond-containing silane coupling agent, acryloyl chloride, glycidyl methacrylate, maleic anhydride and alkenyl succinic anhydride.
The grafting monomer comprises one or a mixture of styrene and methacrylic acid monomers.
The acrylic monomer comprises: acrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, or the like.
The heat-resistant polylactic acid composition is prepared by melt blending of polylactic resin and a starch compound.
The preparation method of the starch compound comprises one of the following steps:
(1) stirring and blending the nucleating agent and the starch graft copolymer emulsion according to a certain solid content ratio, and fully drying to prepare a starch compound;
(2) directly mixing the nucleating agent and the starch graft copolymer at high speed to prepare the starch compound.
Compared with other polylactic acid-based composite materials, the method has the basic idea that the toughness of the polylactic acid is improved by adding the soft starch graft copolymer, and meanwhile, the polylactic acid-based composite material is low in cost and has good degradation performance. And the nucleating agent is added, and the nucleating agent and the starch graft copolymer can promote the dispersion of the nucleating agent and the starch graft copolymer in the polylactic acid by the mutual promotion of the dispersion of the nucleating agent and the starch graft copolymer in the slurry
The invention has the beneficial effects that: in order to determine the performance of the material, the prepared composite material is hot-pressed into a film, and the mechanical property of the material is detected. The composite material obtained by the preparation method provided by the invention has the characteristics of high biomass content, good toughness, biodegradability, good thermal deformation temperature, excellent thermoplastic performance and the like. The polylactic acid-based composite material can be realized on traditional simple synthesis equipment, has low cost and environmental friendliness, and is easy to realize industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of starch graft copolymer
Example 1
(1) And (3) synthesis of modified starch: 100g of starch dried at 80 ℃ for 24h is weighed and placed in a four-neck flask, a certain amount of ethyl acetate and a small amount of pyridine are added into the flask, 3g of acryloyl chloride is dropwise added into the flask after vigorous stirring for a period of time, and heating is not needed in the reaction process. After full reaction, washing with absolute ethyl alcohol, centrifuging and drying to obtain the modified starch.
(2) Preparation of starch graft copolymer: drying the prepared modified starch in a vacuum oven at 60 ℃ for 24 hours, weighing a certain amount of starch, adding the starch into a 500ml four-necked flask, adding a certain amount of deionized water into the four-necked flask, adding ethyl acrylate, stirring at a high speed for pre-emulsification for a period of time, and then beginning to dropwise add potassium persulfate. And cooling the product after the reaction is finished to obtain the starch graft copolymer 1 emulsion. The mass ratio of the modified starch to the ethyl acrylate is 1: 1.
Example 2
(1) And (3) synthesis of modified starch: 100g of starch dried at 80 ℃ for 24h is weighed and placed in a four-necked flask, a certain amount of deionized water is added into the flask, the pH is adjusted to 8-9, 10g of KH570 is dripped into the flask after stirring for a period of time, the reaction temperature is 60 ℃, and the reaction time is 6 h. After full reaction, washing with absolute ethyl alcohol, centrifuging and drying to obtain the modified starch.
(2) Preparation of starch graft copolymer: drying the prepared modified starch in a vacuum oven at 60 ℃ for 24 hours, weighing a certain amount of starch, adding the starch into a 500ml four-necked flask, adding a certain amount of deionized water into the four-necked flask, adding methyl acrylate, stirring at a high speed for pre-emulsification for a period of time, and then beginning to dropwise add potassium persulfate. And cooling the product after the reaction is finished to obtain the starch graft copolymer 2 emulsion. The mass ratio of the modified starch to the methyl acrylate is 1: 3.
Example 3
(1) And (3) synthesis of modified starch: 100g of starch dried at 80 ℃ for 24h is weighed and placed in a four-neck flask, a certain amount of deionized water is added into the flask, the pH is adjusted to 8-9, 6g of GMA is dropwise added into the flask after stirring for a period of time, the reaction temperature is 60 ℃, and the reaction time is 6 h. After full reaction, washing with absolute ethyl alcohol, centrifuging and drying to obtain the modified starch.
(2) Preparation of starch graft copolymer: drying the prepared esterified starch in a vacuum oven at 60 ℃ for 24 hours, weighing a certain amount of starch, adding the starch into a 500ml four-necked flask, adding a certain amount of deionized water into the four-necked flask, adding butyl acrylate and methyl acrylate, stirring at a high speed for pre-emulsification for a period of time, and then beginning to dropwise add potassium persulfate. And cooling the product after the reaction is finished to obtain the starch graft copolymer 3 emulsion. The mass ratio of the modified starch to the methyl acrylate to the butyl acrylate is 1:2: 3.
Example 4
(1) And (3) synthesis of modified starch: 100g of starch dried for 24 hours at 80 ℃ is weighed and placed in a four-neck flask, a certain amount of ethyl acetate and a small amount of pyridine are added into the flask, 4g of acryloyl chloride is dropwise added into the flask after vigorous stirring for a period of time, and heating is not needed in the reaction process. After full reaction, washing with absolute ethyl alcohol, centrifuging and drying to obtain the modified starch.
(2) Preparation of starch graft copolymer: drying the prepared modified starch in a vacuum oven at 60 ℃ for 24 hours, weighing a certain amount of starch, adding the starch into a 500ml four-necked flask, adding a certain amount of deionized water into the four-necked flask, adding ethyl acrylate, pre-emulsifying for a period of time under high-speed stirring, and then beginning to dropwise add potassium persulfate. And cooling the product after the reaction is finished to obtain the starch graft copolymer 4 emulsion. The mass ratio of the modified starch to the ethyl acrylate is 1: 3.
Example 5
(1) And (3) synthesis of modified starch: 100g of starch dried at 80 ℃ for 24h is weighed and placed in a four-necked flask, a certain amount of acetone is added into the flask, and after stirring for a period of time, 6g of dodecyl succinic anhydride is dropwise added into the flask, wherein the reaction temperature is 80 ℃ and the reaction time is 6 h. After full reaction, washing with absolute ethyl alcohol, centrifuging and drying to obtain the modified starch.
(2) Preparation of starch graft copolymer: drying the prepared esterified starch in a vacuum oven at 60 ℃ for 24 hours, weighing a certain amount of starch, adding the starch into a 500ml four-necked flask, adding a certain amount of deionized water into the four-necked flask, adding butyl acrylate and methyl acrylate, stirring at a high speed for pre-emulsification for a period of time, and then beginning to dropwise add potassium persulfate. And cooling the product after the reaction is finished to obtain the starch graft copolymer 5 emulsion. The mass ratio of the modified starch to the styrene to the butyl acrylate is 1:2: 3. Preparation of starch complex
Example 6
And stirring and blending the prepared emulsion of the starch graft copolymer 1 and the nucleating agent EBS according to the solid content ratio of 100:1, stirring at the speed of 500rmp/min for 2h, and drying to prepare the starch compound 1.
Example 7
And stirring and blending the prepared starch graft copolymer 2 emulsion and TMC-328 according to the solid content ratio of 100:5, stirring at the speed of 1000rmp/min for 1h, and drying to prepare the starch compound 2.
Example 8
And stirring and blending the prepared emulsion of the starch graft copolymer 3 and the organic modified montmorillonite according to the solid content ratio of 100:60, stirring at the speed of 1000rmp/min for 1h, and drying to prepare the starch compound 3.
Example 9
And stirring and blending the prepared emulsion of the starch graft copolymer 4 and the organic modified talcum powder according to the solid content ratio of 100:30, stirring at the speed of 400rmp/min for 3h, and drying to prepare the starch compound 4.
Example 10
And stirring and blending the prepared emulsion of the starch graft copolymer 5 and 2-sodium chlorobenzoate according to the solid content ratio of 100:8, stirring at the speed of 400rmp/min for 3h, and drying to prepare the starch compound 5.
Preparation of polylactic acid composition
Example 11
The starch compound 1 prepared in example 6 and polylactic acid are melted and blended according to the mass ratio of 20:80, the processing temperature is 170 ℃, and the blending time is 4 min.
Example 12
The starch compound 2 prepared in example 7 and polylactic acid are subjected to melt blending according to the mass ratio of 10:90, the processing temperature is 165 ℃, and the blending time is 6 min.
Example 13
The starch compound 3 prepared in example 8 and polylactic acid are melted and blended according to the mass ratio of 2:98, the processing temperature is 165 ℃, and the blending time is 6 min.
Example 14
The starch compound 4 prepared in example 9 and polylactic acid are melted and blended according to the mass ratio of 40:60, the processing temperature is 170 ℃, and the blending time is 4 min.
Example 15
The starch compound 5 prepared in example 10 and polylactic acid are subjected to melt blending according to the mass ratio of 5:95, the processing temperature is 170 ℃, and the blending time is 6 min.
Comparative example 1
Weighing 50g of polylactic acid, and carrying out melt blending by using a Haake internal mixer, wherein the processing temperature is 180 ℃, and the blending time is 5 min.
Comparative example 2
The starch graft copolymer prepared in example 1 and polylactic acid are melted and blended according to the mass ratio of 20:80, the processing temperature is 170 ℃, and the blending time is 4 min.
Comparative example 3
The starch graft copolymer prepared in example 2 and polylactic acid are subjected to melt blending according to the mass ratio of 10:90, the processing temperature is 165 ℃, and the blending time is 6 min.
Comparative example 4
The starch graft copolymer prepared in example 3 and polylactic acid are melt blended according to the mass ratio of 5:95, the processing temperature is 165 ℃, and the blending time is 6 min.
Comparative example 5
The starch graft copolymer prepared in example 4 and polylactic acid are melted and blended according to the mass ratio of 40:60, the processing temperature is 170 ℃, and the blending time is 4 min.
Comparative example 6
The starch graft copolymer prepared in example 5 and polylactic acid are subjected to melt blending according to the mass ratio of 5:95, the processing temperature is 170 ℃, and the blending time is 6 min.
The polylactic acid compositions obtained in comparative examples 1 to 6 and examples 11 to 15 were hot-pressed into sheets, and mechanical properties and heat distortion temperature tests were performed, wherein the mechanical property test items include tensile property test and impact property test. The test method and the execution standard selected by the invention are as follows:
the tensile property test is carried out GB/T1040.2-2006, and the tensile rate is 10 mm/min; GB/T1043.1-2008 is executed in the impact performance test, and a simple beam notch sample impact method is adopted; the heat distortion temperature test is carried out according to the national standard GB/T1634. The results are shown in Table 1:
TABLE 1
As shown in Table 1, the heat-resistant polylactic acid composite material obtained by the invention has the advantages of biodegradability, good toughness, high thermal deformation temperature, good component dispersion, low cost and the like, is a green and environment-friendly material, can meet the basic use requirements of the material, and has better application prospects in packaging and other industries. The invention is a breakthrough on the performance of the traditional polylactic acid material.
Claims (10)
1. A heat-resistant polylactic acid composition, wherein the composition comprises a polylactic acid resin and a starch complex; the weight ratio of the starch compound to the polylactic resin is 1: 99-50: 50; the starch compound comprises a starch graft copolymer and a nucleating agent, wherein the weight ratio of the starch graft copolymer to the nucleating agent is 100 (1-100); the starch graft copolymer is prepared by copolymerizing starch treated by a modifier and a graft monomer; the nucleating agent is at least one of an organic nucleating agent and an organic modified inorganic nucleating agent.
2. The heat-resistant polylactic acid composition according to claim 1, wherein the weight ratio of the starch compound to the polylactic acid resin is 2: 98-40: 60; the weight ratio of the starch graft copolymer to the nucleating agent in the starch compound is 100 (1-60).
3. The heat-resistant polylactic acid composition according to claim 1 or 2, wherein the organic nucleating agent is an amide compound, a hydrazide compound, a metal phosphate compound, an organic carboxylic acid and a derivative thereof; the organic modified inorganic nucleating agent is modified talcum powder, montmorillonite, halloysite or attapulgite.
4. The heat-resistant polylactic acid composition according to claim 3, wherein the amide compound is Ethylene Bis Stearamide (EBS), TMC-328 or CZ 500; the hydrazide compound is TMC-300, CHC-300 or TMC-306; the metal phosphate compound is phenyl zinc phosphonate, Sanulant TMHK162 or Sanulant TMHK 160; the organic carboxylic acid and the derivative compound thereof are 2-chlorobenzoic acid sodium salt, tert-butyl aluminum formate, p-tert-butyl aluminum hydroxy benzoate Al-PTBBA or beta-sodium naphthoate.
5. The heat-resistant polylactic acid composition according to claim 1, 2 or 4, wherein the weight ratio of the modifier to the starch is 1:100 to 1:10, and the weight ratio of the modified starch to the graft monomer is 1:1 to 1: 5.
6. The heat-resistant polylactic acid composition according to claim 3, wherein the weight ratio of the modifier to the starch is 1:100 to 1:10, and the weight ratio of the modified starch to the grafting monomer is 1:1 to 1: 5.
7. The heat-resistant polylactic acid composition according to claim 5, wherein the modifier is one or a mixture of two or more of a double bond-containing silane coupling agent, acryloyl chloride, glycidyl methacrylate, maleic anhydride and alkenyl succinic anhydride; the grafting monomer is one or the mixture of styrene and acrylic acid monomer.
8. The heat-resistant polylactic acid composition according to claim 7, wherein the acrylic monomer is acrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate or butyl acrylate.
9. The method for preparing a heat-resistant polylactic acid composition according to any one of claims 1 to 8, wherein the heat-resistant polylactic acid composition is prepared by melt blending of polylactic resin and a starch composite.
10. The method of claim 9, wherein the starch complex is prepared by one of the following steps:
(1) stirring and blending the nucleating agent and the starch graft copolymer emulsion according to a certain solid content ratio, and fully drying to prepare a starch compound;
(2) directly mixing the nucleating agent and the starch graft copolymer at high speed to prepare the starch compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810707445.1A CN108752888B (en) | 2018-07-02 | 2018-07-02 | Heat-resistant polylactic acid composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810707445.1A CN108752888B (en) | 2018-07-02 | 2018-07-02 | Heat-resistant polylactic acid composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108752888A CN108752888A (en) | 2018-11-06 |
| CN108752888B true CN108752888B (en) | 2020-10-30 |
Family
ID=63975573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810707445.1A Active CN108752888B (en) | 2018-07-02 | 2018-07-02 | Heat-resistant polylactic acid composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108752888B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343406A (en) * | 2008-08-18 | 2009-01-14 | 丹阳市华东工程塑料有限公司 | Heat-proof polylactic acid-starch alloy system full-biodegradation material and preparation thereof |
| CN103467947A (en) * | 2013-09-04 | 2013-12-25 | 上海悦萌环保科技有限公司 | Talcum powder nucleating agent-containing crystallized polylactic acid bioplastic |
| CN104610715A (en) * | 2015-01-07 | 2015-05-13 | 惠州市健昇环保材料科技有限公司 | Fiber-reinforced full-degradable heat-resisting environmental protection material, and preparation method and application thereof |
| WO2016099916A1 (en) * | 2014-12-19 | 2016-06-23 | E. I. Du Pont De Nemours And Company | Polylactic acid compositions with accelerated degradation rate and increased heat stability |
| CN105885368A (en) * | 2014-12-12 | 2016-08-24 | 允友成(宿迁)复合新材料有限公司 | Highly heat-resistant polylactic acid/thermoplastic starch composite material and preparation method thereof |
| CN107513258A (en) * | 2016-06-16 | 2017-12-26 | 江南大学 | A kind of high-toughness high-strength starch composite material and preparation method |
-
2018
- 2018-07-02 CN CN201810707445.1A patent/CN108752888B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343406A (en) * | 2008-08-18 | 2009-01-14 | 丹阳市华东工程塑料有限公司 | Heat-proof polylactic acid-starch alloy system full-biodegradation material and preparation thereof |
| CN103467947A (en) * | 2013-09-04 | 2013-12-25 | 上海悦萌环保科技有限公司 | Talcum powder nucleating agent-containing crystallized polylactic acid bioplastic |
| CN105885368A (en) * | 2014-12-12 | 2016-08-24 | 允友成(宿迁)复合新材料有限公司 | Highly heat-resistant polylactic acid/thermoplastic starch composite material and preparation method thereof |
| WO2016099916A1 (en) * | 2014-12-19 | 2016-06-23 | E. I. Du Pont De Nemours And Company | Polylactic acid compositions with accelerated degradation rate and increased heat stability |
| CN104610715A (en) * | 2015-01-07 | 2015-05-13 | 惠州市健昇环保材料科技有限公司 | Fiber-reinforced full-degradable heat-resisting environmental protection material, and preparation method and application thereof |
| CN107513258A (en) * | 2016-06-16 | 2017-12-26 | 江南大学 | A kind of high-toughness high-strength starch composite material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108752888A (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Fabrication, characterization, and application of biocomposites from poly (lactic acid) with renewable rice husk as reinforcement | |
| TWI396712B (en) | Resin composition and the molding article | |
| CN111718566A (en) | PLA/PBAT biodegradable composite material and product thereof | |
| Luan et al. | “One pot” homogeneous synthesis of thermoplastic cellulose acetate-graft-poly (l-lactide) copolymers from unmodified cellulose | |
| JP5565469B2 (en) | POLYLACTIC ACID RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND MOLDED ARTICLE COMPOSED | |
| CN109337312B (en) | Polylactic acid composite material and preparation method thereof | |
| Wu | Utilization of peanut husks as a filler in aliphatic–aromatic polyesters: Preparation, characterization, and biodegradability | |
| CN108948690A (en) | A kind of polylactic acid-lignin-starch composite material and preparation method thereof | |
| Liu et al. | Fabrication of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) biocomposite reinforced wood fiber modified with mixed coupling agents CS-201 and KH550 | |
| CN111205604A (en) | Ultrathin high-strength high-toughness biodegradable mulching film material and film, and preparation method and application thereof | |
| JP5509588B2 (en) | Resin composition and molded article using the same | |
| CN108841153B (en) | High-toughness and high-heat-deformation-temperature polylactic acid composition and preparation method thereof | |
| CN114058168B (en) | High-barrier toughened polylactic acid composite material and preparation method thereof | |
| CN108752888B (en) | Heat-resistant polylactic acid composition and preparation method thereof | |
| Kiangkitiwan et al. | Poly (lactic acid) filled with cassava starch-g-soybean oil maleate | |
| CN112159579A (en) | Functional degradable material with controllable degradation period and preparation method thereof | |
| CN111607209B (en) | High-performance polypropylene carbonate composition and preparation method thereof | |
| CN111763410A (en) | Biodegradable PBAT alloy with high starch content and preparation method thereof | |
| CN108641318B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method thereof | |
| CN107759990B (en) | Full-bio-based polylactic acid composite material and preparation method thereof | |
| CN113308100B (en) | Biodegradable polylactic acid/lignin composite material, preparation method and application | |
| CN110483935B (en) | Polypropylene macromolecule rigidity-increasing nucleating agent and preparation method and application thereof | |
| CN108559238B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof | |
| Song et al. | A facile strategy for the preparation of end-capped and cross-linkable poly (propylene carbonate) with high performance | |
| CN115594961B (en) | High-toughness heat-resistant polylactic acid 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 |