CN105001489A - Bio-based polyolefin composite material and preparation method therefor - Google Patents
Bio-based polyolefin composite material and preparation method therefor Download PDFInfo
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- C08L23/14—Copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention discloses a bio-based polyolefin composite material which comprises the following raw materials in parts by weight: 30-60 parts of modified blue algae, 25-40 parts of polyolefin, 5-20 parts of a reactive plasticizer, 5-10 parts of a bulking agent, 1-5 parts of a lubricant and 0.1-0.5 parts of an antioxidant. The raw materials are mixed and subjected to extrusion and granulation through a co-rotating twin-screw extruder to prepare the bio-based polyolefin composite material. The composite material is good in component compatibility and excellent in mechanical property, and has a very wide application prospect; and the dependence on a petroleum-based material can be reduced, the white pollution is alleviated, a treatment method for turning blue algae into wealth is provided during algal bloom outbreak, and the ecological environment is protected.
Description
Technical field
The present invention relates to bio-based technical field of polymer materials, especially relate to one and prepare composite polyolefine material by adding modification blue-green algae.
Background technology
Plastics oneself be widely used in each department of national economy, this is mainly because it has the advantages such as lightweight, satisfactory mechanical property, water-fast resistance to chemical attack, good looking appearance, making and installation be convenient and cheap; According to statistics, nearly 100,000,000 tons of the plastics ultimate production in the annual world, this accounts for greatly more than 75% of three large synthetic materials total amounts, reaches 92% with the volumetric production ratio of iron and steel.But the chemical stability of conventional plastic is fine, almost can not be degraded at occurring in nature, when plastics industry to a certain extent time, abandoned plastic garbage is just more and more, has almost arrived the degree be seen everywhere, therefore, the hidden danger that plastics itself exist comes out gradually; Such as in China; non-returnable container plastic material is as in 1/3; the annual plastic garbage just having more than 70 ten thousand tons produces; simultaneously; owing to lacking effective taking back and process system, relevant special management regulation and economic policy, " white pollution " is caused to become international environment protection and social concern.
An effective way of administering " white pollution " is exploitation bio-degradable plastics, and it can be dealt with problems from root, is therefore more and more paid attention to.Bio-degradable plastics has premium properties in use, can be decomposed completely again, be finally broken down into the macromolecular material of an integral part to occurring in nature Carbon cycle after discarded by microorganism.Its advantage mainly contains: by compost, finally returns the earth; Reduce and arbitrarily abandon the harm that wildlife is caused; During decomposition, volume reduces gradually, alleviates the pressure of refuse landfill; During burning, thermal value is low, little to the harm of environment and the mankind.But as more expensive in prices such as poly(lactic acid), polyhydroxyalkanoate, poly butylene succinate and poly-hexanodioic acid/butylene terephthalate and the performance comparatively conventional plastic of the degradable plastics of real meaning, as polypropylene and polyethylene have certain gap, limit its large-scale development and application.Be subject to the attention of countries in the world with the matrix material that the filling-modified Polymer materialspreparation of the degradation material such as plant amylum, plant protein obtains Partial digestion, the method meets the theory of resources conservation, economical, environment protection; But the starch of plant origin and protein, the weighting agent being used as matrix material as W-Gum, soyflour and soybean protein isolate etc. can cause food price to go up, and affects animal feed markets, and takies more agriculture plantation.
Along with the quick growth of economy and population, body eutrophication phenomenon is day by day serious, blue-green alga bloom phenomenon occurs again and again, the freshwater lakes such as Taihu Lake, Dian Chi, Chaohu have blue algae bloom for several times every year, the blue-green algae of thousands of tons of is had every day to need process, blue-green algae contains the comparatively natural polymers such as abundant protein, polysaccharide, therefore can be used as weighting agent, replaces starch to prepare matrix material; The people such as Mark Ashton Zeller disclose the method for micro-for edible algae (spirulina and chlorella) with high density polyethylene(HDPE) blended hot pressing thermoplastic composite composition, but by the bad dispersibility of simple blended algae in high density polyethylene(HDPE), and be difficult between high density polyethylene(HDPE) and micro-algae produce stronger interface binding force, thus affect the mechanical property of matrix material; On the other hand, glycerine is adopted to have certain water-absorbent as the thermoplastic composite composition obtained by softening agent, and small molecules softening agent easily moves thus affects the performance (Journal of Applied Polymer Science, 130:3263 – 3275,2013) of matrix material.The Chinese invention patent application of publication number CN104114689A discloses a kind of algae thermoplastics; by squeezing fuel-displaced after Chlorella and former Trentepohlia acetylize obtain thermoplastic material; but algal biomass protein content used is lower than 15%, and a large amount of acylating reagent of wet-process modified employing adds production cost.In addition, the softening agent of use can not and microalgae biomass between produce chemical bond, there is the possibility of plasticizer migration equally.
Summary of the invention
For the problems referred to above that prior art exists, the invention provides a kind of bio-based composite polyolefine material and preparation method thereof.The each component compatibility of matrix material of the present invention is good, and excellent in mechanical performance has boundless application prospect; The present invention not only can reduce the dependence to petroleum based material, reduces " white pollution ", more proposes the treatment process that a kind of blue-green algae changes harmful to treasure during algal bloom, be conducive to preserving the ecological environment.
Technical scheme of the present invention is as follows:
A kind of bio-based composite polyolefine material, the parts by weight that described matrix material comprises raw material and each raw material are: modification blue-green algae 30 ~ 60 parts, polyolefine 25 ~ 40 parts, reactive plasticizer 5 ~ 20 parts, expanding material 5 ~ 10 parts, lubricant 1 ~ 5 part, antioxidant 0.1 ~ 0.5 part.
The preparation method of described modification blue-green algae is:
(1) by after fresh blue-green algae microwave drying to water content 1 ~ 10%, 80 ~ 200 orders are crushed to, obtained blue-green algae powder;
(2) take 500 ~ 1000g blue-green algae powder, 5 ~ 100g properties-correcting agent, join in reactor after fully mixing, oil bath is heated to 70 ~ 90 DEG C, stirs under the rotating speed of 20 ~ 50 revs/min, after reaction 1 ~ 3h, and discharging; Described properties-correcting agent is one or more in diacetyl oxide, maleic anhydride, succinyl oxide, positive capryl(yl)chloride;
(3) wash away the properties-correcting agent not participating in reaction with acetone, repeat 3 times, be placed in 80 ~ 200 DEG C of baking ovens and dry to constant weight and obtain modification blue-green algae.
Described blue-green algae is one or more in Microcystis aeruginosa, anabena, spirulina, artrospira spirulina, plan Anabaena, chamber ball algae, tip algae, the algae that quivers, sheet algae, Xi Zao, joint ball algae, chlorella.
The proteinaceous massfraction of described blue-green algae is not less than 30%.
Described polyolefine is one or more in Low Density Polyethylene, high density polyethylene(HDPE), homo-polypropylene, Co-polypropylene.
Described reactive plasticizer is one or more in epoxy soybean oil, epoxy Semen Maydis oil, epoxy sunflower seed oil, epoxy rapeseed oil.
Described expanding material is one or more in ethene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer.
Described lubricant is one or both mixtures in stearic acid, ethylene bis stearic acid amide; Described antioxidant is antioxidant 1010.
A preparation method for bio-based composite polyolefine material, comprises the steps:
(1) by modification blue-green algae 30 ~ 60 parts, polyolefine 25 ~ 40 parts, reactive plasticizer 5 ~ 20 parts, expanding material 5 ~ 10 parts, lubricant 1 ~ 5 part, antioxidant 0.1 ~ 0.5 part is placed in homogenizer and mixes;
(2) by parallel dual-screw extruding machine extruding pelletization, obtained described bio-based composite polyolefine material; Melt blending temperature is 90 ~ 190 DEG C, and screw speed is 200 ~ 600 revs/min.
The technique effect that the present invention is useful is:
1, matrix material of the present invention is by carrying out to harmful blue-green algae the weighting agent that dry method modification makes macromolecular material, and what turn waste into wealth for algal tufa burst period blue-green algae provides a kind of practicable treatment process, is conducive to preserving the ecological environment.
2, matrix material of the present invention adopts blue-green algae to be raw material, and this raw material is simple and easy to get, reduces the preparation cost of matrix material of the present invention, and this composite materials property is excellent simultaneously, can be widely used in the fields such as agricultural, packaging and environmental protection.
3, by dry method, modification is carried out to blue-green algae in preparation process of the present invention, the Algae toxins that can effectively degrade in blue-green algae biomass.
4, making to produce chemical bond between modification blue-green algae and softening agent by adding reaction sexual type softening agent in preparation process of the present invention, reducing the impact of plasticizer migration on composite materials property.
Embodiment
Below in conjunction with embodiment, the present invention is specifically described.
Embodiment 1
A kind of bio-based composite polyolefine material, preparation method is as follows:
(1) be after 10% by fresh Microcystis aeruginosa (protein content is 36%) microwave drying to water content, be crushed to 80 orders, obtained Microcystis aeruginosa powder;
(2) take 1000g Microcystis aeruginosa powder, 50g diacetyl oxide, join in reactor after fully mixing, oil bath is heated to 70 DEG C, stirs under the rotating speed of 50 revs/min, after reaction 3h, and discharging;
(3) wash away the properties-correcting agent diacetyl oxide not participating in reaction with acetone, repeat 3 times, be placed in 190 DEG C of dry 2h of baking oven, obtain modification Microcystis aeruginosa 920g, Algae toxins residual quantity be untreated before 12.7%;
(4) modification Microcystis aeruginosa 800g is got, Low Density Polyethylene 600g, epoxy soybean oil 150g, ethene-vinyl acetate copolymer 150g, stearic acid 35g, antioxidant 1010 6g, be placed in homogenizer to mix, by parallel dual-screw extruding machine (screw diameter 26mm, L/D=46) extruding pelletization, obtained described bio-based composite polyolefine material;
Melt blending temperature is 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, and screw speed is 300 revs/min.
By bio-based polyolefin composite grain obtained above, to put in 10MPa, the vulcanizing press of 180 DEG C hot pressing 5 minutes, the sheet material that cooling room temperature is taken out.The tensile strength recording material is 7.6MPa, and elongation at break is 36.1%.
Embodiment 2
A kind of bio-based composite polyolefine material, preparation method is as follows:
(1) be after 8% by fresh anabena (protein content is 45%) microwave drying to water content, be crushed to 120 orders, obtained anabena powder;
(2) take 1000g anabena powder, 100g maleic anhydride, join in reactor after fully mixing, oil bath is heated to 90 DEG C, stirs under the rotating speed of 20 revs/min, after reaction 2h, and discharging;
(3) wash away the properties-correcting agent maleic anhydride not participating in reaction with acetone, repeat 3 times, be placed in 120 DEG C of dry 3h of baking oven, obtain modification anabena 930g, Algae toxins residual quantity be untreated before 7.3%;
(4) modification anabena 900g is got, Co-polypropylene 500g, epoxy Semen Maydis oil 100g, ethylene-vinyl alcohol copolymer 110g, stearic acid 10g, ethylene bis stearic acid amide 10g, antioxidant 1010 10g, is placed in homogenizer and mixes, by parallel dual-screw extruding machine (screw diameter 26mm, L/D=46) extruding pelletization, obtained described bio-based composite polyolefine material;
Melt blending temperature is 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, and screw speed is 200 revs/min.
By bio-based polyolefin composite grain obtained above, to put in 10MPa, the vulcanizing press of 180 DEG C hot pressing 5 minutes, the sheet material that cooling room temperature is taken out.The tensile strength recording material is 11.2MPa, and elongation at break is 10.6%.
Embodiment 3
A kind of bio-based composite polyolefine material, preparation method is as follows:
(1) be after 3% by fresh spirulina (protein content is 53%) microwave drying to water content, be crushed to 100 orders, obtained spirulina powder;
(2) take 500g spirulina powder, the positive capryl(yl)chloride of 20g, joins after fully mixing in reactor, and oil bath is heated to 80 DEG C, stirs under the rotating speed of 35 revs/min, after reaction 1h, and discharging;
(3) wash away the positive capryl(yl)chloride of the properties-correcting agent not participating in reaction with acetone, repeat 3 times, be placed in 200 DEG C of dry 2h of baking oven, obtain modification spirulina 950g;
(4) modification spirulina 600g is got, high density polyethylene(HDPE) 800g, epoxy soybean oil 400g, ethene-vinyl acetate copolymer 200g, stearic acid 80g, antioxidant 1010 2g, be placed in homogenizer to mix, by parallel dual-screw extruding machine (screw diameter 26mm, L/D=46) extruding pelletization, obtained described bio-based composite polyolefine material;
Melt blending temperature is 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, and screw speed is 500 revs/min.
By bio-based polyolefin composite grain obtained above, to put in 10MPa, the vulcanizing press of 180 DEG C hot pressing 5 minutes, the sheet material that cooling room temperature is taken out.The tensile strength recording material is 13.9MPa, and elongation at break is 27.5%.
Claims (9)
1. a bio-based composite polyolefine material, it is characterized in that the parts by weight that described matrix material comprises raw material and each raw material are: modification blue-green algae 30 ~ 60 parts, polyolefine 25 ~ 40 parts, reactive plasticizer 5 ~ 20 parts, expanding material 5 ~ 10 parts, lubricant 1 ~ 5 part, antioxidant 0.1 ~ 0.5 part.
2. bio-based composite polyolefine material according to claim 1, is characterized in that the preparation method of described modification blue-green algae is:
(1) by after fresh blue-green algae microwave drying to water content 1 ~ 10%, 80 ~ 200 orders are crushed to, obtained blue-green algae powder;
(2) take 500 ~ 1000g blue-green algae powder, 5 ~ 100g properties-correcting agent, join in reactor after fully mixing, oil bath is heated to 70 ~ 90 DEG C, stirs under the rotating speed of 20 ~ 50 revs/min, after reaction 1 ~ 3h, and discharging; Described properties-correcting agent is one or more in diacetyl oxide, maleic anhydride, succinyl oxide, positive capryl(yl)chloride;
(3) wash away the properties-correcting agent not participating in reaction with acetone, repeat 3 times, be placed in 80 ~ 200 DEG C of baking ovens and dry to constant weight and obtain modification blue-green algae.
3. bio-based composite polyolefine material according to claim 2, is characterized in that described blue-green algae is one or more in Microcystis aeruginosa, anabena, spirulina, artrospira spirulina, plan Anabaena, chamber ball algae, tip algae, the algae that quivers, sheet algae, Xi Zao, joint ball algae, chlorella.
4. bio-based composite polyolefine material according to claim 2, is characterized in that the proteinaceous massfraction of described blue-green algae is not less than 30%.
5. bio-based composite polyolefine material according to claim 1, is characterized in that described polyolefine is one or more in Low Density Polyethylene, high density polyethylene(HDPE), homo-polypropylene, Co-polypropylene.
6. bio-based composite polyolefine material according to claim 1, is characterized in that described reactive plasticizer is one or more in epoxy soybean oil, epoxy Semen Maydis oil, epoxy sunflower seed oil, epoxy rapeseed oil.
7. bio-based composite polyolefine material according to claim 1, is characterized in that described expanding material is one or more in ethene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer.
8. bio-based composite polyolefine material according to claim 1, is characterized in that described lubricant is one or both mixtures in stearic acid, ethylene bis stearic acid amide; Described antioxidant is antioxidant 1010.
9. a preparation method for bio-based composite polyolefine material described in claim 1, is characterized in that comprising the steps:
(1) by modification blue-green algae 30 ~ 60 parts, polyolefine 25 ~ 40 parts, reactive plasticizer 5 ~ 20 parts, expanding material 5 ~ 10 parts, lubricant 1 ~ 5 part, antioxidant 0.1 ~ 0.5 part is placed in homogenizer and mixes;
(2) by parallel dual-screw extruding machine extruding pelletization, obtained described bio-based composite polyolefine material; Melt blending temperature is 90 ~ 190 DEG C, and screw speed is 200 ~ 600 revs/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330931A (en) * | 2015-11-03 | 2016-02-17 | 周福海 | Method for preparing polyolefin algae plastic through microwaves |
| CN105331034A (en) * | 2015-11-03 | 2016-02-17 | 周福海 | Method for preparing plastic from algae |
| CN105368088A (en) * | 2015-11-03 | 2016-03-02 | 周福海 | Method for preparing polyolefin composite from algae |
| CN105907066A (en) * | 2016-07-01 | 2016-08-31 | 铜陵方正塑业科技有限公司 | Blue alga based compound biological plastic with nano-calcium nutrient enriched and preparation method of biological plastic |
| CN105968761A (en) * | 2016-07-01 | 2016-09-28 | 铜陵方正塑业科技有限公司 | Layered nano filler montmorillonite modified cyanobacteria-based compound bioplastic and preparation method thereof |
| CN106117999A (en) * | 2016-07-01 | 2016-11-16 | 铜陵方正塑业科技有限公司 | A kind of organic nano bentonite modified cyanophyceae base Biocomposite material and preparation method thereof |
| CN106867175A (en) * | 2017-03-06 | 2017-06-20 | 唐爱兰 | The EVA expanded materials and preparation method of a kind of biomass of blue-green algae containing thermoplasticity |
| CN110591405A (en) * | 2019-09-25 | 2019-12-20 | 东莞市福码鞋材有限公司 | Green alga environment-friendly sole material and preparation method thereof |
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| CN104725727A (en) * | 2015-04-16 | 2015-06-24 | 无锡太湖蓝藻资源应用技术研究院有限公司 | Polypropylene composite containing microalgae and preparing method thereof |
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| CN104479369A (en) * | 2014-12-19 | 2015-04-01 | 无锡太湖蓝藻资源应用技术研究院有限公司 | Degradable plastic containing algae protein and preparation method of degradable plastic |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330931A (en) * | 2015-11-03 | 2016-02-17 | 周福海 | Method for preparing polyolefin algae plastic through microwaves |
| CN105331034A (en) * | 2015-11-03 | 2016-02-17 | 周福海 | Method for preparing plastic from algae |
| CN105368088A (en) * | 2015-11-03 | 2016-03-02 | 周福海 | Method for preparing polyolefin composite from algae |
| CN105330931B (en) * | 2015-11-03 | 2018-06-08 | 周福海 | A kind of method that microwave prepares polyolefin algal plastics |
| CN105907066A (en) * | 2016-07-01 | 2016-08-31 | 铜陵方正塑业科技有限公司 | Blue alga based compound biological plastic with nano-calcium nutrient enriched and preparation method of biological plastic |
| CN105968761A (en) * | 2016-07-01 | 2016-09-28 | 铜陵方正塑业科技有限公司 | Layered nano filler montmorillonite modified cyanobacteria-based compound bioplastic and preparation method thereof |
| CN106117999A (en) * | 2016-07-01 | 2016-11-16 | 铜陵方正塑业科技有限公司 | A kind of organic nano bentonite modified cyanophyceae base Biocomposite material and preparation method thereof |
| CN106867175A (en) * | 2017-03-06 | 2017-06-20 | 唐爱兰 | The EVA expanded materials and preparation method of a kind of biomass of blue-green algae containing thermoplasticity |
| CN110591405A (en) * | 2019-09-25 | 2019-12-20 | 东莞市福码鞋材有限公司 | Green alga environment-friendly sole material and preparation method thereof |
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Application publication date: 20151028 |