CA2306959A1 - A plant fiber composite material, its products and a processing method thereof - Google Patents
A plant fiber composite material, its products and a processing method thereof Download PDFInfo
- Publication number
- CA2306959A1 CA2306959A1 CA002306959A CA2306959A CA2306959A1 CA 2306959 A1 CA2306959 A1 CA 2306959A1 CA 002306959 A CA002306959 A CA 002306959A CA 2306959 A CA2306959 A CA 2306959A CA 2306959 A1 CA2306959 A1 CA 2306959A1
- Authority
- CA
- Canada
- Prior art keywords
- plant fiber
- composite material
- fiber composite
- weight
- parts
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/007—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and at least partly composed of recycled material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/28—Moulding or pressing characterised by using extrusion presses
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2311/00—Use of natural products or their composites, not provided for in groups B29K2201/00 - B29K2309/00, as reinforcement
- B29K2311/10—Natural fibres, e.g. wool or cotton
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Forests & Forestry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
There is disclosed a plant fiber composite material that is environmentally benign. There is also disclosed products of the plant fiber composite material, a processing method for the plant fiber composite material, and extruded or molded products using the plant fiber composite material.
Description
A PLANT FIBER COMPOSITE MATERIAL, ITS PRODUCTS
AND A PROCESSING METHOD THEREOF
TECHNICAL FIELD OF THE INVENTION
This invention relates to a plant fiber composite material, more particularly to an environmentally benign plant fiber composite material. This invention also relates to the products of the composite material and a processing method for the plant fiber composite material and extruded or molded products using the plant fiber composite material.
BACKGROUND OF THE INVENTION
To eliminate "white pollution", substitutes for plastics and foamed plastics have been searched for all over the world, particularly focusing on disposable tableware and products made from plant fiber. At present, there are more than 100 disclosed patent technologies of disposable tableware and products utilizing plant fiber as major raw material in the world such as in the United States, Japan, Germany, Switzerland, Thailand etc, in which more than 60 patent technologies were disclosed in China. However, only a few have commenced commercial production, and the type of products have not been put into market in a large scale for substitution of plastics and foamed plastics. The first reason is the higher cost of the product using plant fiber for raw material, because the plant fiber will result in heavier weight of products, take fast food lunch box for an example, each foamed plastic fast food lunch box only weighs 5 g, each paper lunch box weighs 25 g, and each plant fiber lunch box weighs 50 g, and the cost is greatly decided by the material weight. The second reason is the dark color being disliked or unacceptable by the consumers and the third reason is the poor quality that will result in higher damage rate in transportation or utilization.
However, viewing from current disclosed patent technologies, although the material formulations of various disposable tableware and products and/or appliances are not identical, three processing methods {"slurrying mould", 'vet cold pressing" and "Dry hot pressing"
technologies) have been adopted predaminantly. However, all of the three processing methods are intermittent processes, and are unable to form a continuous streamlined production process.
SU~'Ii~tARY OF THE INVENTION
One object of the inventicm is to provide a plant fiber composite material with a biodegradation function, that is an ecological environment protection material.
Another object of the invention is to provide an application of the plant fiber composite material in manufacturing tableware, products, and/or appliances.
A further object of the invention is to provide a processing method of the plant fiber composite material in tableware, products, and/or appliance fabrication, that is a continuous streamlined production process.
The plant fiber composite material of the invention comprises the following components in relative weight parts (by weight in parts):
plant fiber 60-80 parts polycarbonate resin 5-30 parts food coloring agent 0-5 parts wherein the molecular weight of said polycarbonate resin is 8000-35000.
The plant fiber of the invention is obtained from a crop waste, including, but not limited to rice husk, ricegrass, wheat bran, wheat straw, beanstalk, cotton stalk, forage grass, peanut shell, cornstalk, sorghum stalk, bagasse, coconut shell, residue of sugarcane, residue of orange juice, sawed timber bits, bamboo ash and the mixtures thereof. The amount of said plant fiber is preferably in the range of 70 to 80 parts by weight.
Preferably, the polycarbonatE; resin of the invention is polymerized 2,2' (4 hydroxylphenyl) propane carbonate monomer.
Preferably, the molecular weight of the polycarbonate resin is 10000-15000, and the amount of the polycarbonate resin is in the range of 15 to 20 parts by weight.
The food coloring agent of the invention is selected from the group consisting of titanium white, zinc oxide, iron oxide red, pil,~rnent yellow 147, pigment blue 15, and combinations thereof.
Preferably, the food coloring agent is titanium white. Preferably, the amount of the food coloring agent is in the range of 4 to 5 parts by weight.
The plant fiber composite material of the invention can further comprises 5-15 weight parts of 4,4'-biphenyl methane diisocyanate (MDI), and preferably 3-5 parts by weight.
The processing method of continuous streamlined production process for production of tableware, products, and/or appliances using plant fiber composite material of the invention comprises the following steps:
1. Place the pulverized plant fiber into the hopper of plant fiber expander, add water corresponding to 10-30% of the plant fiber by weight into the expanding chamber, turn on the expander, and then the plant fiber is expanded and prepared into a powder;
2. Place above expanded plant fiber powder, polycarbonate resin, food coloring agent and /or MDI proportionally into a vertical stirring mixer, thoroughly mix them for 10 min to form a mixture, then add the mixture into a granulator, and the granules of the plant fiber composite material is prepared under 120-200 °C.
AND A PROCESSING METHOD THEREOF
TECHNICAL FIELD OF THE INVENTION
This invention relates to a plant fiber composite material, more particularly to an environmentally benign plant fiber composite material. This invention also relates to the products of the composite material and a processing method for the plant fiber composite material and extruded or molded products using the plant fiber composite material.
BACKGROUND OF THE INVENTION
To eliminate "white pollution", substitutes for plastics and foamed plastics have been searched for all over the world, particularly focusing on disposable tableware and products made from plant fiber. At present, there are more than 100 disclosed patent technologies of disposable tableware and products utilizing plant fiber as major raw material in the world such as in the United States, Japan, Germany, Switzerland, Thailand etc, in which more than 60 patent technologies were disclosed in China. However, only a few have commenced commercial production, and the type of products have not been put into market in a large scale for substitution of plastics and foamed plastics. The first reason is the higher cost of the product using plant fiber for raw material, because the plant fiber will result in heavier weight of products, take fast food lunch box for an example, each foamed plastic fast food lunch box only weighs 5 g, each paper lunch box weighs 25 g, and each plant fiber lunch box weighs 50 g, and the cost is greatly decided by the material weight. The second reason is the dark color being disliked or unacceptable by the consumers and the third reason is the poor quality that will result in higher damage rate in transportation or utilization.
However, viewing from current disclosed patent technologies, although the material formulations of various disposable tableware and products and/or appliances are not identical, three processing methods {"slurrying mould", 'vet cold pressing" and "Dry hot pressing"
technologies) have been adopted predaminantly. However, all of the three processing methods are intermittent processes, and are unable to form a continuous streamlined production process.
SU~'Ii~tARY OF THE INVENTION
One object of the inventicm is to provide a plant fiber composite material with a biodegradation function, that is an ecological environment protection material.
Another object of the invention is to provide an application of the plant fiber composite material in manufacturing tableware, products, and/or appliances.
A further object of the invention is to provide a processing method of the plant fiber composite material in tableware, products, and/or appliance fabrication, that is a continuous streamlined production process.
The plant fiber composite material of the invention comprises the following components in relative weight parts (by weight in parts):
plant fiber 60-80 parts polycarbonate resin 5-30 parts food coloring agent 0-5 parts wherein the molecular weight of said polycarbonate resin is 8000-35000.
The plant fiber of the invention is obtained from a crop waste, including, but not limited to rice husk, ricegrass, wheat bran, wheat straw, beanstalk, cotton stalk, forage grass, peanut shell, cornstalk, sorghum stalk, bagasse, coconut shell, residue of sugarcane, residue of orange juice, sawed timber bits, bamboo ash and the mixtures thereof. The amount of said plant fiber is preferably in the range of 70 to 80 parts by weight.
Preferably, the polycarbonatE; resin of the invention is polymerized 2,2' (4 hydroxylphenyl) propane carbonate monomer.
Preferably, the molecular weight of the polycarbonate resin is 10000-15000, and the amount of the polycarbonate resin is in the range of 15 to 20 parts by weight.
The food coloring agent of the invention is selected from the group consisting of titanium white, zinc oxide, iron oxide red, pil,~rnent yellow 147, pigment blue 15, and combinations thereof.
Preferably, the food coloring agent is titanium white. Preferably, the amount of the food coloring agent is in the range of 4 to 5 parts by weight.
The plant fiber composite material of the invention can further comprises 5-15 weight parts of 4,4'-biphenyl methane diisocyanate (MDI), and preferably 3-5 parts by weight.
The processing method of continuous streamlined production process for production of tableware, products, and/or appliances using plant fiber composite material of the invention comprises the following steps:
1. Place the pulverized plant fiber into the hopper of plant fiber expander, add water corresponding to 10-30% of the plant fiber by weight into the expanding chamber, turn on the expander, and then the plant fiber is expanded and prepared into a powder;
2. Place above expanded plant fiber powder, polycarbonate resin, food coloring agent and /or MDI proportionally into a vertical stirring mixer, thoroughly mix them for 10 min to form a mixture, then add the mixture into a granulator, and the granules of the plant fiber composite material is prepared under 120-200 °C.
3. Place above granules into a bunter of the hopper of a twin-screw extruder, control the extrusion processing technologies parameters of the twin-screw extruder as follows to extrude the granules into a sheet continuously:
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-lOm/min 4. Continuously convey above extruded sheet to a puncher connected with the twin-screw extruder, and then punch and mold they sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, to obtain the final products.
In the invention, the size of said expanded plant fiber powder is 10-120 mesh, preferably 20-40 mesh, water content of the expanded plant fiber powder is 20-50%, preferably 30%.
Preferably in this invention, the processing technological parameters of extruding the granules of the plant fiber composite material in the twin-screw extruder are as follows:
cylinder temperature 220 °C
connector temperature 230 °C
die temperature 250 °C
extrusion pressure 25 Mpa.
Said extruded sheet is a plate sheet or an open heterotypic sheet.
The invention will be better understood on reading the following detailed description of non-limiting embodiments of the invention with reference to the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
Figurel is a schematic diagram of the continuous streamlined fabrication of crop waste composite material products of the invention.
DETAILED DESCRIPTION OF THfE INVENTION
Example 1 Preparation of plant fiber composite granules According to the composition formulation of plant fiber composite material shown as table 1, granulation is conducted on plant fiber composite material of each formulation according to the following steps:
1. Expansion: dry the plant fiber, delivered the dried plant fiber into a DP-120 type Plant fiber expander 1 produced by Shenyang Grain and Oil Machinery Works and expand them to be 20-40 mesh powder having micro holes with water content of 10%.
2. Granulation: place the expanded plant fiber powder, polycarbonate resin (produced by Changzhou Chemical Works), titanium white and/or MDI of said formulation into a conventional vertical stirring mixer 2, thoroughly mixed for about 10 min to form a mixture, then place the mixture into a granulator for granulation at 170 °C to obtain the granules of the fiber composite material having water content 10%.
Table 1 Composition Formula Formula Formula Formula Formula (kg) fig) fig) fig) fig) Plant scraps 20 20 22.5 12.5 17.5 Polycarbonate 2.5 3.75 1.25 6.25 1.25 resin Titanium white I 1.25 1.25 3.75 2.5 MDI 1.25 1.25 2.5 3.75 Example 2 Preparation of the tableware using plant fiber composite material Place the granules of the plant fiber composite material of the example 1 into the hopper 4 of a conventional twin-screw extruder 5, and then extrude the granules according to the extrusion technological processing parameters shown in table 2. During the extrusion process, after the granular entering into the cylinder from the hopper 4, under the action of rotary compaction and mixing of the twin-screw 5 at said cylinder temperature, the granules were transformed from a solid state to an uniform continuous melt having a definite flowability, and the uniform continuos melt was passed through a perforated plate into a narrow gap die to be molded into a high temperature sheet under the rotary compaction of the twin-screv~~ 5. A puncher 7 having nominal one ton pressure was installed 100 mm ahead of the twin-screw extruder 5 directly, and the upper and lower moulds of which were preheated to 180 °C. While the high temperature sheet was pushed to the place between the upper and lower moulds of the puncher 7 by the extruder's head, the upper mould was punched dow and the sheet was punched into the required product. Every punching action took about 3 seconds, in which actions of cut-off, side-cut were finished simultaneously. Then, the punched product was carried away by a conveyor belt for shape fixing and cooling.
From the quality and cost of the product, it is concluded that the product of test 1 is preferred.
Table 2 Group Formula Cylinder Connector Die Extrusion Extrusion ing temperaturetemperaturetemperaturepressure speed (C) (C) (C) (Mpa) (m/min) Test Formula 220 230 250 25 2 1 1 ~
Test Formula 227.5 242.5 262.5 25 2 2 3 ~
Test Formula 235 255 275 25 2 Test Formula 242.5 267.5 287.5 25 2 4 5 ~
Text Formula 250 280 300 25 2 Example 3 Conventional performance test of products of plant fiber composite material Sample: Disposable instant noodle bowl produced by the plant fiber composite material of formula 1 of the example 1.
Test standard:
1. GB 5009.60-85: Analysis of sanitary standards of polyethylene, polystyrene, and polypropylene formed products for food packing 2. GB 9683-88: Sanitary standards of composite food packing bags 3. TB/T2611-94: Universal technological conditions of railway fast food lunch box product supply Table 3:
Test items Measured Normalized value value n-hexane evaporated residue mg/L 7.2 <_30 4% acetic acid evaporated residue1.7 530 m,~'L
65% alcohol evaporated residue 6.3 530 mg/L
Consumption of potassium permanganate9.0 <_10 mg/L
Heavy metal (account for Pb) mg/L<1 Sl Loading test (%) 0.8 <_5 Buffet oil decoloring test Negative Negative Alcohol decoloring test Negative Negative Oil resistant test No leak No leak Water resistant test No leak No leak Folding test Qualified No fracture under foldings Fluorescent test (254nm and 365nm)Qualified SScm2/104cmz I ~
As shown in table 3, ii was indicated that the conventional performance of the products of the invention could reach the requirements of related test standards. Mention may be made of the product's low evaporated residue of n-hexane, 4% acetic acid and 65% alcohol.
_ Example 4 Biodegradation test of the product of plant fiber composite material Institution in charge of detection: Chinese Research Academy of Environmental Science, Institute of Solids Testing method: According to the plastic testing method of U.S. ASTM D5338-92 standard of aerobic biodegradation under the condition of controlled composting process, measure the COz yield per unit weight of plastic and rice husk tableware sample within an interval time.
Testing model: Select the disposable tableware produced by formula 1 of example 1 as testing group, and degradable PE plastic film, degradable PS plastic tableware as control group.
Testing results: COZ yield of each gram of disposable tableware in the testing group was 590 mg within 32 days, while C02 yield of each gram of degradable PE plastic film in the control group was 480 mg after 32 days, and COZ yield of each gram of degradable PS
plastic tableware in the control group was 290 mg in the: same period. Consequently, in comparison of above three C02 yields, it was indicated that the disposable tableware in the testing group had better degradability than the degradable PE plastic film, degradable PS plastic tableware in control group obviously, and meanwhile it could be observed that there were massive white myeotic spots in the tableware sample of the testing group and the toughness of the tableware sample of the testing group was significantly reduced during and after the testing process.
Example 5 Acute toxicity test of the products of plant fiber composite material of the invention Sample: disposable tableware produced by formula 1 of example 1 Institution in charge of detection: State Environment Protection Administration of China, Beijing Institute of Environmental Medicine Testing standard: refer to the requirements of toxicological detection in "Universal technological conditions of railway fast food lunchbox product supply"
(TB/2611-94) in Professional Standard of the Ministry of Railways in the People's Republic of China, in which the sample is pretreated as follows: Weigh 30 g of sample and shear the sample into pieces of 0.5 cmX0.5 cm. Put the sheared pieces into four sorbitic extractors, then respectively add 300m1 of distilled water, 300m1 of 4% acetic acid, 300m1 of 65% alcohol, and 300m1 of n-hexane into each extractor. Heat each extractor to the boiling points of above four solvents and reflux them for 2 hr, in which the extractor containing water and extractor containing 4% acetic acid were put into paraffin bathes, while the extractor containing 65% alcohol and extractor containing n-hexane were put into water bathes). Mix the four reflux liquids uniformly to form a mixture, and then place above mixture into a rotary evaporator and depressurize concentrate it at 70-75 °C to obtain a concentrated liquid. Take 100 ml the concentrated liquid, add 2 g of starch into it, and then heat it to be paste for experimental use.
Testing method: experimental animal is Kunming breed mice weighing 13-22 g each, provided by the Animal Center of Chinese Academy of Medical Sciences.
( 1 ) Trial test: 9 male and female mice randomly divided into three groups separately, 3 mice in each group. Contamination dosages were 20 g/kg, 19 g/kg, S g/kg, respectively. The animals were contaminated (dosed) through gastric lavage via mouth.
(2) Formal test: 40 male and female mice were randomly divided into four groups respectively, 10 animals in each group. According to the results of trail test, contamination dosages were 20 g/kg, 10 g/kg, 5 g/kg, and 2.5 g/kg, once contaminated through gastric lavage via mouth. The animals were fasted for 12 hr before gastric lavage. The maximum volume of a dose was 0.4 ml; 20 g of body weight. The animals were obsen~ed for one week after contamination (dosing) and poisoning symptoms of animals and time of death were recorded. If the LDSO was more than 10 g/l:g, it need not be calculated. If the LDSO was less than 10 g/kg, it was determined through a retest using a probability unit-graph method.
Experimental results:
( 1 ) Trial test: no death resulted in three dosage groups of male and female animals, and no poisoning symptoms could be seen.
(2) Formal test: no death resulted in four dosage groups of male and female animals, and no poisoning symptoms could be seer.
Measured LDSO of delivered samples for detection was more than 20 g/kg.
Results: lethal dose of ~0% (LDso) of above concentrated liquid was more than 20 g/kg.
Thus, according to acute toxicity (LDS~) grade scale, it belongs to actual non-toxic grade.
Plant fiber composite material of the invention is tasteless, odorless, and nontoxic. It is an ecologically benign environmentally benign plant fiber composite material. The products made with the plant fiber composite material of the invention demonstrated cold-resistance, heat-resistance, acid-resistance, and alkali-resistance. The major advantages of the product are high impact resistance, high durability, small creep, and stable product size. T'he product can be hydrolyzed and broken easily in long term submergence in water, and can be disintegrated to become a powder under long term embedded underground with no pollution to soil.
In summary, the above embodiments are only for describing the invention but not for limiting the range of the invention. All the changes that do not depart from the spirit of this invention are within the range of this :invention.
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-lOm/min 4. Continuously convey above extruded sheet to a puncher connected with the twin-screw extruder, and then punch and mold they sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, to obtain the final products.
In the invention, the size of said expanded plant fiber powder is 10-120 mesh, preferably 20-40 mesh, water content of the expanded plant fiber powder is 20-50%, preferably 30%.
Preferably in this invention, the processing technological parameters of extruding the granules of the plant fiber composite material in the twin-screw extruder are as follows:
cylinder temperature 220 °C
connector temperature 230 °C
die temperature 250 °C
extrusion pressure 25 Mpa.
Said extruded sheet is a plate sheet or an open heterotypic sheet.
The invention will be better understood on reading the following detailed description of non-limiting embodiments of the invention with reference to the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
Figurel is a schematic diagram of the continuous streamlined fabrication of crop waste composite material products of the invention.
DETAILED DESCRIPTION OF THfE INVENTION
Example 1 Preparation of plant fiber composite granules According to the composition formulation of plant fiber composite material shown as table 1, granulation is conducted on plant fiber composite material of each formulation according to the following steps:
1. Expansion: dry the plant fiber, delivered the dried plant fiber into a DP-120 type Plant fiber expander 1 produced by Shenyang Grain and Oil Machinery Works and expand them to be 20-40 mesh powder having micro holes with water content of 10%.
2. Granulation: place the expanded plant fiber powder, polycarbonate resin (produced by Changzhou Chemical Works), titanium white and/or MDI of said formulation into a conventional vertical stirring mixer 2, thoroughly mixed for about 10 min to form a mixture, then place the mixture into a granulator for granulation at 170 °C to obtain the granules of the fiber composite material having water content 10%.
Table 1 Composition Formula Formula Formula Formula Formula (kg) fig) fig) fig) fig) Plant scraps 20 20 22.5 12.5 17.5 Polycarbonate 2.5 3.75 1.25 6.25 1.25 resin Titanium white I 1.25 1.25 3.75 2.5 MDI 1.25 1.25 2.5 3.75 Example 2 Preparation of the tableware using plant fiber composite material Place the granules of the plant fiber composite material of the example 1 into the hopper 4 of a conventional twin-screw extruder 5, and then extrude the granules according to the extrusion technological processing parameters shown in table 2. During the extrusion process, after the granular entering into the cylinder from the hopper 4, under the action of rotary compaction and mixing of the twin-screw 5 at said cylinder temperature, the granules were transformed from a solid state to an uniform continuous melt having a definite flowability, and the uniform continuos melt was passed through a perforated plate into a narrow gap die to be molded into a high temperature sheet under the rotary compaction of the twin-screv~~ 5. A puncher 7 having nominal one ton pressure was installed 100 mm ahead of the twin-screw extruder 5 directly, and the upper and lower moulds of which were preheated to 180 °C. While the high temperature sheet was pushed to the place between the upper and lower moulds of the puncher 7 by the extruder's head, the upper mould was punched dow and the sheet was punched into the required product. Every punching action took about 3 seconds, in which actions of cut-off, side-cut were finished simultaneously. Then, the punched product was carried away by a conveyor belt for shape fixing and cooling.
From the quality and cost of the product, it is concluded that the product of test 1 is preferred.
Table 2 Group Formula Cylinder Connector Die Extrusion Extrusion ing temperaturetemperaturetemperaturepressure speed (C) (C) (C) (Mpa) (m/min) Test Formula 220 230 250 25 2 1 1 ~
Test Formula 227.5 242.5 262.5 25 2 2 3 ~
Test Formula 235 255 275 25 2 Test Formula 242.5 267.5 287.5 25 2 4 5 ~
Text Formula 250 280 300 25 2 Example 3 Conventional performance test of products of plant fiber composite material Sample: Disposable instant noodle bowl produced by the plant fiber composite material of formula 1 of the example 1.
Test standard:
1. GB 5009.60-85: Analysis of sanitary standards of polyethylene, polystyrene, and polypropylene formed products for food packing 2. GB 9683-88: Sanitary standards of composite food packing bags 3. TB/T2611-94: Universal technological conditions of railway fast food lunch box product supply Table 3:
Test items Measured Normalized value value n-hexane evaporated residue mg/L 7.2 <_30 4% acetic acid evaporated residue1.7 530 m,~'L
65% alcohol evaporated residue 6.3 530 mg/L
Consumption of potassium permanganate9.0 <_10 mg/L
Heavy metal (account for Pb) mg/L<1 Sl Loading test (%) 0.8 <_5 Buffet oil decoloring test Negative Negative Alcohol decoloring test Negative Negative Oil resistant test No leak No leak Water resistant test No leak No leak Folding test Qualified No fracture under foldings Fluorescent test (254nm and 365nm)Qualified SScm2/104cmz I ~
As shown in table 3, ii was indicated that the conventional performance of the products of the invention could reach the requirements of related test standards. Mention may be made of the product's low evaporated residue of n-hexane, 4% acetic acid and 65% alcohol.
_ Example 4 Biodegradation test of the product of plant fiber composite material Institution in charge of detection: Chinese Research Academy of Environmental Science, Institute of Solids Testing method: According to the plastic testing method of U.S. ASTM D5338-92 standard of aerobic biodegradation under the condition of controlled composting process, measure the COz yield per unit weight of plastic and rice husk tableware sample within an interval time.
Testing model: Select the disposable tableware produced by formula 1 of example 1 as testing group, and degradable PE plastic film, degradable PS plastic tableware as control group.
Testing results: COZ yield of each gram of disposable tableware in the testing group was 590 mg within 32 days, while C02 yield of each gram of degradable PE plastic film in the control group was 480 mg after 32 days, and COZ yield of each gram of degradable PS
plastic tableware in the control group was 290 mg in the: same period. Consequently, in comparison of above three C02 yields, it was indicated that the disposable tableware in the testing group had better degradability than the degradable PE plastic film, degradable PS plastic tableware in control group obviously, and meanwhile it could be observed that there were massive white myeotic spots in the tableware sample of the testing group and the toughness of the tableware sample of the testing group was significantly reduced during and after the testing process.
Example 5 Acute toxicity test of the products of plant fiber composite material of the invention Sample: disposable tableware produced by formula 1 of example 1 Institution in charge of detection: State Environment Protection Administration of China, Beijing Institute of Environmental Medicine Testing standard: refer to the requirements of toxicological detection in "Universal technological conditions of railway fast food lunchbox product supply"
(TB/2611-94) in Professional Standard of the Ministry of Railways in the People's Republic of China, in which the sample is pretreated as follows: Weigh 30 g of sample and shear the sample into pieces of 0.5 cmX0.5 cm. Put the sheared pieces into four sorbitic extractors, then respectively add 300m1 of distilled water, 300m1 of 4% acetic acid, 300m1 of 65% alcohol, and 300m1 of n-hexane into each extractor. Heat each extractor to the boiling points of above four solvents and reflux them for 2 hr, in which the extractor containing water and extractor containing 4% acetic acid were put into paraffin bathes, while the extractor containing 65% alcohol and extractor containing n-hexane were put into water bathes). Mix the four reflux liquids uniformly to form a mixture, and then place above mixture into a rotary evaporator and depressurize concentrate it at 70-75 °C to obtain a concentrated liquid. Take 100 ml the concentrated liquid, add 2 g of starch into it, and then heat it to be paste for experimental use.
Testing method: experimental animal is Kunming breed mice weighing 13-22 g each, provided by the Animal Center of Chinese Academy of Medical Sciences.
( 1 ) Trial test: 9 male and female mice randomly divided into three groups separately, 3 mice in each group. Contamination dosages were 20 g/kg, 19 g/kg, S g/kg, respectively. The animals were contaminated (dosed) through gastric lavage via mouth.
(2) Formal test: 40 male and female mice were randomly divided into four groups respectively, 10 animals in each group. According to the results of trail test, contamination dosages were 20 g/kg, 10 g/kg, 5 g/kg, and 2.5 g/kg, once contaminated through gastric lavage via mouth. The animals were fasted for 12 hr before gastric lavage. The maximum volume of a dose was 0.4 ml; 20 g of body weight. The animals were obsen~ed for one week after contamination (dosing) and poisoning symptoms of animals and time of death were recorded. If the LDSO was more than 10 g/l:g, it need not be calculated. If the LDSO was less than 10 g/kg, it was determined through a retest using a probability unit-graph method.
Experimental results:
( 1 ) Trial test: no death resulted in three dosage groups of male and female animals, and no poisoning symptoms could be seen.
(2) Formal test: no death resulted in four dosage groups of male and female animals, and no poisoning symptoms could be seer.
Measured LDSO of delivered samples for detection was more than 20 g/kg.
Results: lethal dose of ~0% (LDso) of above concentrated liquid was more than 20 g/kg.
Thus, according to acute toxicity (LDS~) grade scale, it belongs to actual non-toxic grade.
Plant fiber composite material of the invention is tasteless, odorless, and nontoxic. It is an ecologically benign environmentally benign plant fiber composite material. The products made with the plant fiber composite material of the invention demonstrated cold-resistance, heat-resistance, acid-resistance, and alkali-resistance. The major advantages of the product are high impact resistance, high durability, small creep, and stable product size. T'he product can be hydrolyzed and broken easily in long term submergence in water, and can be disintegrated to become a powder under long term embedded underground with no pollution to soil.
In summary, the above embodiments are only for describing the invention but not for limiting the range of the invention. All the changes that do not depart from the spirit of this invention are within the range of this :invention.
Claims (21)
1. A plant fiber composite material, which comprises the following components parts by weight:
plant fiber 60-80 parts polycarbonate resin 5-30 parts food coloring agent 0-5 parts wherein the molecular weight of said polycarbonate resin is 8000-35000.
plant fiber 60-80 parts polycarbonate resin 5-30 parts food coloring agent 0-5 parts wherein the molecular weight of said polycarbonate resin is 8000-35000.
2. The plant fiber composite material according to claim 1, wherein said plant fiber component is selected from the group consisting of rice husk, ricegrass, wheat bran, wheat straw, bean stalk, cotton stalk, forage grass, peanut shell, corn stalk, sorghum stalk, sugarcane residue, coconut shell, residue of orange juice, sugarcane residue, sawed timber bits, bamboo ash, and mixtures thereof.
3. The plant fiber composite material according to claim 1, wherein the amount of the plant fiber component is in the range of 70 to 80 parts by weight.
4. The plant fiber composite material according to claim 1, wherein said polycarbonate resin is composed of 2,2'-di (4-hydroxylphenyl) propane carbonate monomer.
5. The plant fiber composite material according to claim 1, wherein the amount of the polycarbonate resin s in the range of 15 to 20 parts by weight.
6. The plant fiber composite material according to claim 1, wherein the molecular weight of the polycarbonate resin is 10,000-15,000.
7. The plant fiber composite material according to claim 1, wherein the amount of the food coloring agent is in the range of 2 to 5 parts by weight.
8. The plant fiber composite material according to claim 1, wherein the food coloring agent is selected from the group consisting of titanium white, zinc oxide, iron oxide red, pigment yellow 147, pigment blue 15, and combinations thereof.
9. The plant fiber composite material according to claim 8, wherein the food coloring agent is titanium white.
10. The plant fiber composite material according to claim 1, wherein the composite material further comprises 5-15 weight parts of 4,4'-biphenyl methane diisocyanate.
11. The plant fiber composite material according to claim 10, wherein the amount of 4,4'-biphenyl methane diisocyanate is in the range of 3 to 5 parts by weight.
12. A process for fabricating tableware, products, and appliances using the plant fiber composite material of claim 1, comprising:
(1) placing a plant fiber material into a hopper containing a plant fiber expander chamber, adding water corresponding to 10-30% of the plant fiber material (by weight) into the expander chamber, and fuming on the expander, so as to obtain an expanded plant fiber powder;
(2) placing the expanded plant fiber powder, polycarbonate resin, food coloring agent and/or 4,4'-biphenyl methane diisocyanate proportionally into a vertical stirring mixer, thoroughly mixing for 10 min to form a mixture, then adding the mixture into a granulator to prepare plant fiber composite material under °C in the form of granules;
(3) placing the granules of plant fiber composite material into a hopper of a twin-screw extruder, controlling the extrusion processing technologies parameters of the twin-screw extruder to extrude the granules into sheet continuously:
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-10 m/min (4) continuously conveying above extruded sheet to a puncher connected with the twin-screw extruder, and then punching and molding the extruded sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, so as to obtain the fabricated or molded products.
(1) placing a plant fiber material into a hopper containing a plant fiber expander chamber, adding water corresponding to 10-30% of the plant fiber material (by weight) into the expander chamber, and fuming on the expander, so as to obtain an expanded plant fiber powder;
(2) placing the expanded plant fiber powder, polycarbonate resin, food coloring agent and/or 4,4'-biphenyl methane diisocyanate proportionally into a vertical stirring mixer, thoroughly mixing for 10 min to form a mixture, then adding the mixture into a granulator to prepare plant fiber composite material under °C in the form of granules;
(3) placing the granules of plant fiber composite material into a hopper of a twin-screw extruder, controlling the extrusion processing technologies parameters of the twin-screw extruder to extrude the granules into sheet continuously:
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-10 m/min (4) continuously conveying above extruded sheet to a puncher connected with the twin-screw extruder, and then punching and molding the extruded sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, so as to obtain the fabricated or molded products.
13. The process according to claim 12, wherein the size of the expanded plant fiber powder is 10-120 mesh.
14. The process according to claim 13, wherein the size of the expanded plant fiber powder is about 20-40 mesh.
15. The process according to claim 12, wherein the water content of the plant fiber expanded powder is 20-50% (by weight).
16. The process of claim 15 wherein the water content of the plant fiber expanded powder is about 30% (by weight).
17. The processing method according to claim 12, wherein the processing technological parameters of the twin-screw extruder are cylinder temperature is 220 °C, connector temperature is 2:30 °C, and die temperature is 250 °C, extrusion pressure is 25 Mpa.
18. The processing method according to claim 12, wherein said extruded sheet is a plate sheet or an open heterotypic sheet.
19. The processing method according to claim 12, wherein the moulds temperature of puncher is about 180 °C.
20. A method for using a plant fiber composite according to claim 1 for molding or extruding of tableware, products, and/or appliances, comprising:
(1) placing the granules of plant fiber composite material into a hopper of a twin-screw extruder, controlling the extrusion processing technologies parameters of the twin-screw extruder to extrude the granules into sheet continuously:
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-10 m/min (2) continuously conveying above extruded sheet to a puncher connected with the twin-screw extruder, and then punching and molding the extruded sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, so as to obtain the fabricated or molded products.
(1) placing the granules of plant fiber composite material into a hopper of a twin-screw extruder, controlling the extrusion processing technologies parameters of the twin-screw extruder to extrude the granules into sheet continuously:
cylinder temperature 220-250 °C
connector temperature 230-280 °C
die temperature 250-300 °C
extrusion pressure 15-30 Mpa extrusion speed 1-10 m/min (2) continuously conveying above extruded sheet to a puncher connected with the twin-screw extruder, and then punching and molding the extruded sheet with heated moulds at 150-250 °C, 2-50 kg/cm2, so as to obtain the fabricated or molded products.
21. A polymeric tableware product or appliance comprising a plant fiber composite material according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002306959A CA2306959A1 (en) | 2000-03-31 | 2000-04-26 | A plant fiber composite material, its products and a processing method thereof |
| EP01936215A EP1294811A2 (en) | 2000-03-31 | 2001-04-02 | A plant composite material, its processing and use |
| AU2001262187A AU2001262187A1 (en) | 2000-03-31 | 2001-04-02 | A plant fiber composite material, its products and a processing method thereof |
| PCT/EP2001/004071 WO2001072904A2 (en) | 2000-03-31 | 2001-04-02 | A plant composite material, its processing and use |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/540,484 US6624217B1 (en) | 2000-03-31 | 2000-03-31 | Plant fiber composite material, its products and a processing method thereof |
| CA002306959A CA2306959A1 (en) | 2000-03-31 | 2000-04-26 | A plant fiber composite material, its products and a processing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2306959A1 true CA2306959A1 (en) | 2001-10-26 |
Family
ID=25681762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002306959A Abandoned CA2306959A1 (en) | 2000-03-31 | 2000-04-26 | A plant fiber composite material, its products and a processing method thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1294811A2 (en) |
| AU (1) | AU2001262187A1 (en) |
| CA (1) | CA2306959A1 (en) |
| WO (1) | WO2001072904A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374233A (en) * | 2012-04-25 | 2013-10-30 | 李霞 | Environment-friendly plant cellulose tableware |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323819C (en) * | 2004-12-13 | 2007-07-04 | 东南大学 | Artificial board of straw non-wood plant fibre and its preparation process |
| CN1325570C (en) * | 2004-12-13 | 2007-07-11 | 东南大学 | Compostte artificial board and its preparation method |
| GB2449507A (en) * | 2007-07-25 | 2008-11-26 | Procurasell Holdings Ltd | Method and apparatus for manufacturing a food packaging container |
| CN101824227B (en) * | 2009-03-06 | 2011-09-14 | 西南科技大学 | Thermoplastic plant fiber/carbon dioxide-based plastic blending material and preparation method thereof |
| CN102001118B (en) * | 2010-09-25 | 2013-08-07 | 朱文华 | Device and method for manufacturing disposable wooden tableware and liner |
| CN102528881B (en) * | 2011-12-15 | 2015-01-07 | 宁波意斯欧国际贸易有限公司 | Vegetable fiber tableware and preparation method thereof |
| FR2996998B1 (en) * | 2012-10-18 | 2016-01-22 | Nicolas Saverino | SEAFOOD PLATTER |
| CN103627196B (en) * | 2013-12-02 | 2016-07-06 | 安徽易科环保科技有限公司 | Degradable plant fibre daily utensil and manufacture method thereof |
| NL1042071B1 (en) * | 2016-09-23 | 2018-04-04 | Handelsonderneming We Ha | Method and device for the manufacture of wood composite |
| CN114836018B (en) * | 2022-06-20 | 2023-07-07 | 深圳市博彩新材料科技有限公司 | Pearlescent PC color master batch with reinforcing and toughening effects and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116965A (en) * | 1984-07-04 | 1986-01-24 | Karupu Kogyo Kk | Composite resin sheet |
| US5354621A (en) * | 1992-07-02 | 1994-10-11 | Beltec International | Biodegradable construction material and manufacturing method |
| GB9309917D0 (en) * | 1993-05-14 | 1993-06-30 | Stemform Prod Ltd | Moulding composition |
| DE19500283A1 (en) * | 1994-01-08 | 1995-07-20 | Stewing Nachrichtentechnik | Prodn. of biodegradable articles with wood-like character |
| CN1114663A (en) * | 1995-06-02 | 1996-01-10 | 武汉顺天泰集团股份有限公司 | Method for producing composite high molecular material filter core of engine oil filter |
| US5948524A (en) * | 1996-01-08 | 1999-09-07 | Andersen Corporation | Advanced engineering resin and wood fiber composite |
-
2000
- 2000-04-26 CA CA002306959A patent/CA2306959A1/en not_active Abandoned
-
2001
- 2001-04-02 EP EP01936215A patent/EP1294811A2/en not_active Withdrawn
- 2001-04-02 WO PCT/EP2001/004071 patent/WO2001072904A2/en not_active Ceased
- 2001-04-02 AU AU2001262187A patent/AU2001262187A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374233A (en) * | 2012-04-25 | 2013-10-30 | 李霞 | Environment-friendly plant cellulose tableware |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001072904A3 (en) | 2002-05-16 |
| WO2001072904A2 (en) | 2001-10-04 |
| EP1294811A2 (en) | 2003-03-26 |
| AU2001262187A1 (en) | 2001-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6624217B1 (en) | Plant fiber composite material, its products and a processing method thereof | |
| CN100469836C (en) | biodegradable polymer | |
| KR20120103158A (en) | Composition for biodegradable plastic and biodegradable plastic goods molded by the composition | |
| KR102300547B1 (en) | Biodegradable Plastic Composite using Livestock Organic Resource and Manufacturing Method thereof | |
| CA2306959A1 (en) | A plant fiber composite material, its products and a processing method thereof | |
| CN102634072A (en) | Degradable thermoplastic rubber membrane using agricultural plant resources as main material and preparation method of degradable thermoplastic rubber membrane | |
| CN101654528B (en) | Biodegradable resin for agricultural film and production method thereof | |
| CN107099060A (en) | A kind of environmental type starch base completely biodegradable material and its article fabrication methods | |
| CN109370244A (en) | Degradable plant fiber disposable tableware and preparation method thereof | |
| WO2008028356A1 (en) | Inorganic material combination reinforced, heat-resistant biodegradable masterbatch pellets and its preparation | |
| CN100572433C (en) | A kind of production method of fully biodegradable plastic resin and film products thereof | |
| CN100358981C (en) | Granular fuel with crop straw and production thereof | |
| KR20020090679A (en) | Composit of natural biodegradable materials and method for manufacturing natural biodegradable goods | |
| CN105295408A (en) | Environment-friendly type coated paper preparation technology | |
| CN112430382A (en) | Compostable full-degradable disposable tableware and preparation method thereof | |
| JP4837834B2 (en) | Biodegradable plastic molded product mixed with food residue charcoal | |
| EP1142958A1 (en) | A plant fiber composite material, its products and a processing method thereof | |
| CN110982293A (en) | Degradable environment-friendly packaging material | |
| CN113402780A (en) | Sheet-grade full-biodegradable polyester | |
| CN1995137A (en) | Biodegradable high polymer foaming material, foam article and its production method | |
| CN1315471A (en) | Plant fiber composite material, product thereof and manufacturing method thereof | |
| KR100545045B1 (en) | Method for manufacturing molded articles made of biodegradable materials using waste paper | |
| CN109942949A (en) | A kind of biological plastics and preparation method being suitable for instant degradation in seawater | |
| JP2004209878A (en) | Biodegradable preform and its manufacturing method | |
| CN102408588A (en) | Full-biodegradable resin prepared from non-staple grain plant modified starch and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |