CN110054838A - A kind of cellulose hydridization filler enhancing polymer composites and preparation method thereof - Google Patents
A kind of cellulose hydridization filler enhancing polymer composites and preparation method thereof Download PDFInfo
- Publication number
- CN110054838A CN110054838A CN201910343478.7A CN201910343478A CN110054838A CN 110054838 A CN110054838 A CN 110054838A CN 201910343478 A CN201910343478 A CN 201910343478A CN 110054838 A CN110054838 A CN 110054838A
- Authority
- CN
- China
- Prior art keywords
- hydridization filler
- agriculture
- micro
- cellulose
- forestry organic
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of cellulose hydridization filler enhancing polymer composites and preparation method thereof, and raw material is as follows: 100 parts of polymeric matrix；5 parts of compatilizer；Hilllock stone waste/1~40 part of agriculture and forestry organic waste material hydridization filler.Preparation method, comprising: (1) hilllock stone waste and agriculture and forestry organic waste material are blended, by adding water to be configured to aqueous dispersions；(2) it mills aqueous dispersions, micro-nano hydridization filler dispersion liquid is made；(3) micro-nano hydridization filler solution is filtered, and is dried, and is mechanically pulverized, micro-nano hydridization filler powder is made；(4) micro-nano hydridization filler powder is pressed and is blended, and stir with polymer, compatilizer；(5) by mixture machine extruding pelletization, and corresponding product is made by injection molding machine injection moulding.The present invention has the advantages that rationally and effectively realizing its higher value application, problem of environmental pollution is avoided, effective solution cellulose is easy to the problem of reuniting in non-polar polymer, assigns polymer composites excellent mechanical property.
Description
Technical field
The present invention relates to polymer composites technical field, in particular to a kind of artificial hilllock carbolic acid calcium waste residue/agricultural
Waste hydridization filler enhances polymer composites and preparation method.
Background technique
Artificial hilllock stone be using macromolecule, inorganic gel agent or both mixture as jointing material, with lithotome particle,
Aluminium hydrate powder etc. is main raw material(s), is added pigment and other adjuvants, the processes such as agitated mixing, condensation cure process and
At stone material.The artificial hilllock stone of resin base be using the particle of marble, lime stone etc., powder as main raw material(s), using resin as
Artificial stone made of jointing material.A large amount of waste residue can be generated in artificial hilllock stone process, the main component of waste residue is carbonic acid
Calcium and unsaturated polyester (UP), these waste residues are difficult to secondary operation of degrading and be unable to, and dealing with improperly can cause environmental pollution.
Agriculture and forestry organic waste material refers to the organic species being dropped in entire agricultural production process, as agricultural crop straw, bagasse,
Rice husk, bark etc..Contain a large amount of native cellulose in agriculture and forestry organic waste material, is a kind of important biomass resource, China is agriculture
The continuous accumulation of state, sparetime university, agriculture and forestry organic waste material occupies a large amount of arable land, and peasant mostly uses greatly the mode of burning to solve the problems, such as, long
This can cause serious pollution to environment in the past.Agriculture and forestry organic waste material energy conversion utilizes the research hotspot for being field of renewable energy
One of.
Cellulose is rich in agriculture and forestry organic waste material, such as stalk, bagasse material, due to cellulose hydrogen bond rich in, easily
It is difficult to remove in formation intramolecular hydrogen bond, realizes micro nanometer fiber, this makes cellulose for non-polar polymer
When enhancing, the dispersion in non-polar polymer matrix is undesirable, is easy to assemble each other, causes agglomeration, make
Obtaining composite materials property cannot be promoted.Therefore improve interfacial interaction between cellulose and polymeric matrix for
The application of cellulose enhancing composite material is of great significance.Mostly use solvent displacement, addition surfactant, original position greatly at present
Polymerization directly carries out the modified interfacial interaction for improving cellulose and polymeric matrix in surface to cellulose, but improves
Effect it is often not ideal enough, and the use of organic solvent not only results in environmental pollution, also increases cost, it is difficult to use
In actual production.Therefore, develop a kind of low cost, nonhazardous, environmental-friendly cellulose enhancing polymer preparation method tool
There is very important realistic meaning.
Summary of the invention
The present invention in view of the drawbacks of the prior art, provide a kind of cellulose hydridization filler enhancing polymer composites and
Preparation method can effectively solve the above-mentioned problems of the prior art.
In order to realize the above goal of the invention, the technical solution adopted by the present invention is as follows:
A kind of cellulose hydridization filler enhancing polymer composites, raw material are as follows:
The raw material parts is parts by weight unless otherwise specified.
100 parts of polymeric matrix；
5 parts of compatilizer；
Hilllock stone waste/1~40 part of agriculture and forestry organic waste material hydridization filler.
The matter of hilllock stone waste and agriculture and forestry organic waste material hydridization filler in the hilllock stone waste/agriculture and forestry organic waste material hydridization filler
Amount is than being 1:1~2:1.
Further, the hilllock stone waste is artificial hilllock carbolic acid calcium waste residue；Agriculture and forestry organic waste material is stalk slag or dry sugarcane
Slag；Polymeric matrix is the non-polar polymers such as polypropylene.
Further, hilllock stone waste/agriculture and forestry organic waste material hydridization filler mesh number is 200~500 mesh.
Further, the polymer composites, raw material are as follows: 100 parts of polypropylene, 5 parts of compatilizer, hilllock stone is discarded
The mass ratio of object/10 parts of agriculture and forestry organic waste material hydridization filler, hilllock stone waste and agriculture and forestry organic waste material hydridization filler is 3:2.
The invention also discloses the preparation methods of above-mentioned filler enhancing polymer composites, comprising the following steps:
(1) artificial hilllock carbolic acid calcium waste residue powder is blended by a certain percentage with agriculture and forestry organic waste materials such as stalk, bagasses, is passed through
Water is added to be configured to the aqueous dispersions that mass percent concentration is 0.5%~2%；
(2) it is repeatedly milled aqueous dispersions obtained in step (1) using mechanical disruption mode, realizes the agricultures such as stalk, bagasse
Micro-nano hydridization filler dispersion liquid is made in woods waste micro nanometer fiber；
(3) micro-nano hydridization filler solution obtained in step (2) is filtered, and is dried at 100 DEG C~120 DEG C
2~3 hours, and be further mechanically pulverized by high speed disintegrator, micro-nano hydridization filler powder is made；
(4) micro-nano hydridization filler powder obtained in step (3) is blended by a certain percentage with polymer, compatilizer,
And 10~20min is stirred by high-speed mixer；
(5) it by obtained mixture in step (4) by double screw extruder extruding pelletization, and is injected by injection molding machine
Corresponding product is made in molding.
Compared with prior art the present invention has the advantages that
(1) present invention uses artificial hilllock stone waste and agriculture and forestry organic waste material, by being used for enhancing polymer composite
Material, rationally and effectively realizes its higher value application, avoids problem of environmental pollution.
(2) present invention is milled using multistage shearing machine and realizes the agriculture and forestry organic waste materials micro nanometer fiber such as stalk, bagasse, together
When introduce the removing of waste calcium carbonate auxiliary fiber element, using in waste calcium carbonate oxygen-containing group and stalk, bagasse etc. naturally
Micro-nano hydridization filler is prepared in the interaction of hydrogen bond between hydroxyl on cellulose.Contain in artificial hilllock stone waste residue big
Unsaturated polyester (UP) is measured, the interfacial interaction between cellulose and non-polar polymer substrate can be increased, improves cellulose and exists
Dispersion in polymeric matrix, effective solution cellulose are easy to the problem of reuniting in non-polar polymer, assign poly-
The excellent mechanical property of compound composite material.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, by the following examples, to the present invention do into
One step is described in detail.
Embodiment 1:
100 parts of polypropylene are weighed by quality, 5 parts of compatilizer, the agricultural such as artificial hilllock carbolic acid calcium waste residue and stalk, bagasse are useless
The mass ratio of gurry is 3:2, hilllock stone waste/5 parts of agriculture and forestry organic waste material hydridization filler.
The agriculture and forestry organic waste materials such as artificial hilllock carbolic acid calcium waste residue powder and stalk, bagasse are blended according to the ratio of 1:2 first,
Prepare the aqueous solution that mass percent concentration is 5%.It mills by multistage shearing machine, realizes that the agricultural such as stalk, bagasse are discarded
Object micro nanometer fiber is made micro-nano hydridization filler dispersion liquid, then micro-nano hydridization filler solution is filtered, and is placed in
It is dried 3 hours at 120 DEG C in baking oven, micro-nano hydridization filler powder is made with high speed disintegrator crushing, powder mesh number is 300
Then mesh polypropylene is blended in proportion with micro-nano hydridization filler powder, be added in high-speed mixer and stir 10min, then
Pass through double screw extruder extruding pelletization, the setting of extruder screw temperature are as follows: 170/180/185/190/190/180 DEG C, screw rod
Revolving speed is 100rpm, is then molded under the conditions of 190 DEG C by injection molding machine and dumbbell shape standard tensile test bars are made.
Embodiment 2:
100 parts of polypropylene are weighed by quality, 5 parts of compatilizer, the agricultural such as artificial hilllock carbolic acid calcium waste residue and stalk, bagasse are useless
The mass ratio of gurry is 3:2, hilllock stone waste/10 parts of agriculture and forestry organic waste material hydridization filler.Preparation process is the same as embodiment 1.
Embodiment 3:
100 parts of polypropylene are weighed by quality, 5 parts of compatilizer, the agricultural such as artificial hilllock carbolic acid calcium waste residue and stalk, bagasse are useless
The mass ratio of gurry is 3:2, hilllock stone waste/20 parts of agriculture and forestry organic waste material hydridization filler.Preparation process is the same as embodiment 1.
Comparative example 1:
100 parts of polypropylene are weighed by quality, preparation process is the same as embodiment 1.
1 inspection result of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Tensile strength (MPa) | 35.8 | 41.6 | 39.3 | 31.4 |
| Elongation at break (%) | 48 | 32 | 18 | 76 |
| Young's modulus (MPa) | 1067.8 | 1176.8 | 1668.6 | 1270.2 |
| Impact strength (kJ/m2) | 10.8 | 11.4 | 14.8 | 9.3 |
As it can be seen from table 1 a kind of artificial hilllock carbolic acid calcium waste residue prepared by the present invention/agriculture and forestry organic waste material hydridization filler increases
Strength polymer composite material has superior mechanical property.
Those of ordinary skill in the art will understand that the embodiments described herein, which is to help reader, understands this hair
Bright implementation method, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.Ability
The those of ordinary skill in domain disclosed the technical disclosures can make its various for not departing from essence of the invention according to the present invention
Its various specific variations and combinations, these variations and combinations are still within the scope of the present invention.
Claims (5)
1. a kind of cellulose hydridization filler enhances polymer composites, it is characterised in that: the original of the polymer composites
Expect as follows:
The raw material parts is parts by weight unless otherwise specified；
100 parts of polymeric matrix；
5 parts of compatilizer；
Hilllock stone waste/1~40 part of agriculture and forestry organic waste material hydridization filler；
The mass ratio of hilllock stone waste and agriculture and forestry organic waste material hydridization filler in the hilllock stone waste/agriculture and forestry organic waste material hydridization filler
For 1:1~2:1.
2. a kind of cellulose hydridization filler according to claim 1 enhances polymer composites, it is characterised in that: described
Hilllock stone waste is artificial hilllock carbolic acid calcium waste residue；Agriculture and forestry organic waste material is stalk slag or bagasse；Polymeric matrix is polypropylene
Equal non-polar polymers.
3. a kind of cellulose hydridization filler according to claim 2 enhances polymer composites, it is characterised in that: hilllock stone
Waste/agriculture and forestry organic waste material hydridization filler mesh number is 200~500 mesh.
4. a kind of cellulose hydridization filler according to claim 1 enhances polymer composites, it is characterised in that: described
Polymer composites, raw material are as follows: 100 parts of polypropylene, 5 parts of compatilizer, hilllock stone waste/agriculture and forestry organic waste material hydridization filler 10
Part, the mass ratio of hilllock stone waste and agriculture and forestry organic waste material hydridization filler is 3:2.
5. a kind of preparation method of cellulose hydridization filler enhancing polymer composites according to claim 1, special
Sign is: the following steps are included:
(1) artificial hilllock carbolic acid calcium waste residue powder is blended by a certain percentage with agriculture and forestry organic waste materials such as stalk, bagasses, by adding water
It is configured to the aqueous dispersions that mass percent concentration is 0.5%~2%；
(2) it is repeatedly milled aqueous dispersions obtained in step (1) using mechanical disruption mode, realizes that the agricultural such as stalk, bagasse are useless
Micro-nano hydridization filler dispersion liquid is made in gurry micro nanometer fiber；
(3) micro-nano hydridization filler solution obtained in step (2) is filtered, and dries 2~3 at 100 DEG C~120 DEG C
Hour, and be further mechanically pulverized by high speed disintegrator, micro-nano hydridization filler powder is made；
(4) micro-nano hydridization filler powder obtained in step (3) is blended by a certain percentage with polymer, compatilizer, and led to
It crosses high-speed mixer and stirs 10~20min；
(5) it by obtained mixture in step (4) by double screw extruder extruding pelletization, and is injection moulded by injection molding machine
Corresponding product is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910343478.7A CN110054838B (en) | 2019-04-26 | 2019-04-26 | Cellulose hybrid filler reinforced polymer composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910343478.7A CN110054838B (en) | 2019-04-26 | 2019-04-26 | Cellulose hybrid filler reinforced polymer composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110054838A true CN110054838A (en) | 2019-07-26 |
| CN110054838B CN110054838B (en) | 2021-04-13 |
Family
ID=67321134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910343478.7A Active CN110054838B (en) | 2019-04-26 | 2019-04-26 | Cellulose hybrid filler reinforced polymer composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110054838B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362789A (en) * | 2020-04-23 | 2020-07-03 | 贺州学院 | Method for synthesizing calcium formate from waste residue of artificial granite |
| CN112724512A (en) * | 2020-12-23 | 2021-04-30 | 北京理工大学 | Preparation method of nano-cellulose polypropylene master batch |
| CN115745524A (en) * | 2022-12-06 | 2023-03-07 | 四川大学 | Artificial organic stone waste residue-micro-nano cellulose hybrid reinforced material and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153241A (en) * | 1985-05-29 | 1992-10-06 | Beshay Alphons D | Polymer composites based cellulose-VI |
| CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
| WO2006066041A1 (en) * | 2004-12-13 | 2006-06-22 | Agri-Polymerix, Llc | Biopolymer and methods of making it |
| CN101500960A (en) * | 2006-07-24 | 2009-08-05 | 第一毛织株式会社 | Marble chip, method for preparing the same and artificial marble using the same |
| US20110015308A1 (en) * | 2006-11-03 | 2011-01-20 | Polyone Corporation | Colorant concentrates for thermoplastic biofiber composites |
| CN102245681A (en) * | 2008-12-15 | 2011-11-16 | 第一毛织株式会社 | Marble chips for an artificial marble, manufacturing method thereof, and artificial marble comprising same |
| CN103724898A (en) * | 2013-12-09 | 2014-04-16 | 南京理工大学 | Polymer based nanocomposite and preparing method thereof |
| CN106189325A (en) * | 2016-08-04 | 2016-12-07 | 南京工业大学 | A kind of lignin enhancement mode Wood-plastic material and preparation method thereof |
| CN106336583A (en) * | 2016-08-26 | 2017-01-18 | 江苏上上电缆集团有限公司 | Cable insulation material and preparation method thereof |
| CN107686665A (en) * | 2017-10-10 | 2018-02-13 | 袁春华 | A kind of enhanced wood plastic composite and preparation method thereof |
-
2019
- 2019-04-26 CN CN201910343478.7A patent/CN110054838B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153241A (en) * | 1985-05-29 | 1992-10-06 | Beshay Alphons D | Polymer composites based cellulose-VI |
| CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
| WO2006066041A1 (en) * | 2004-12-13 | 2006-06-22 | Agri-Polymerix, Llc | Biopolymer and methods of making it |
| CN101500960A (en) * | 2006-07-24 | 2009-08-05 | 第一毛织株式会社 | Marble chip, method for preparing the same and artificial marble using the same |
| US20110015308A1 (en) * | 2006-11-03 | 2011-01-20 | Polyone Corporation | Colorant concentrates for thermoplastic biofiber composites |
| CN102245681A (en) * | 2008-12-15 | 2011-11-16 | 第一毛织株式会社 | Marble chips for an artificial marble, manufacturing method thereof, and artificial marble comprising same |
| CN103724898A (en) * | 2013-12-09 | 2014-04-16 | 南京理工大学 | Polymer based nanocomposite and preparing method thereof |
| CN106189325A (en) * | 2016-08-04 | 2016-12-07 | 南京工业大学 | A kind of lignin enhancement mode Wood-plastic material and preparation method thereof |
| CN106336583A (en) * | 2016-08-26 | 2017-01-18 | 江苏上上电缆集团有限公司 | Cable insulation material and preparation method thereof |
| CN107686665A (en) * | 2017-10-10 | 2018-02-13 | 袁春华 | A kind of enhanced wood plastic composite and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 何录菊: "表面改性对三种天然纤维增强聚丙烯复合材料拉伸性能的对比研究", 《科学技术与工程》 * |
| 吴巧妹: "无机纳米相纳米纤维素杂化纳米材料的研究进展", 《生物质化学工程》 * |
| 李忠正主编: "《植物纤维资源化学》", 30 June 2012, 中国轻工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362789A (en) * | 2020-04-23 | 2020-07-03 | 贺州学院 | Method for synthesizing calcium formate from waste residue of artificial granite |
| CN112724512A (en) * | 2020-12-23 | 2021-04-30 | 北京理工大学 | Preparation method of nano-cellulose polypropylene master batch |
| CN115745524A (en) * | 2022-12-06 | 2023-03-07 | 四川大学 | Artificial organic stone waste residue-micro-nano cellulose hybrid reinforced material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110054838B (en) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110054838A (en) | A kind of cellulose hydridization filler enhancing polymer composites and preparation method thereof | |
| US20070259584A1 (en) | Biodegradable polymer composites and related methods | |
| US9783679B2 (en) | Microstructured composite material, method for the production thereof, moulded articles made thereof and also purposes of use | |
| CN103131150B (en) | Polypropylene/polylactic acid/starch composite material and preparation method thereof | |
| CN109825045B (en) | Graphene composite biomass reinforced PBS/PBAT biodegradable composite material and preparation method thereof | |
| Taurino et al. | Use of different kinds of waste in the construction of new polymer composites | |
| CN103059596A (en) | Nano-reinforced wood-plastic composite and preparation method thereof | |
| JP2007217611A (en) | Biodegradable resin composition and molded product | |
| CN102838860A (en) | Formula and preparation method of wood-plastic composite material | |
| CN108948689B (en) | Polylactic acid-lignin composite material modified by reactive extrusion method and preparation method thereof | |
| CN112961474A (en) | Preparation method of polylactic acid/epoxy vegetable oil all-bio-based composite material | |
| CN101824229A (en) | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof | |
| CN104725705A (en) | Method for preparing novel polyethylene wood-plastic composite material | |
| JP6489481B2 (en) | Thermoplastic resin composition and method for producing thermoplastic resin composition | |
| CN101824228B (en) | Thermoplastic plant fiber/polyhydroxyalkanoates blending material and preparation method thereof | |
| CN105949807B (en) | Polyvinyl alcohol-based wood-plastic composite material and melting processing method thereof | |
| CN101029418A (en) | Active non-lignocellulose plant fibre, its production and use | |
| WO2019150907A1 (en) | Cellulose fiber master batch, cellulose fiber-containing resin composition, method for producing cellulose fiber master batch, method for producing cellulose fiber-containing resin composition, and molded body of cellulose fiber-containing resin composition | |
| US11236230B2 (en) | Chlorinated poly(propylene carbonate)/biomass composite material and method for preparing the same | |
| Niu et al. | Preparation, structure, and property of wood flour incorporated polypropylene composites prepared by a solid‐state mechanochemical method | |
| Zhang et al. | Mechanical and interfacial properties of poly (vinyl chloride) based composites reinforced by cassava stillage residue with different surface treatments | |
| CN108948630B (en) | Polyolefin-lignin composite material modified by reactive extrusion method and preparation method thereof | |
| CN101717497A (en) | Bio-based compatilizer, preparation method and application thereof | |
| CN107759990A (en) | A kind of full biological poly lactic acid composite and preparation method thereof | |
| JP2011178877A (en) | Process for manufacturing charcoal-containing resin, charcoal-containing resin, molded product, process for manufacturing carbonized molded product and carbonized molded product |
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 |