CN101143965A - Method for preparing plant protein/inorganic mineral nano composite material - Google Patents
Method for preparing plant protein/inorganic mineral nano composite material Download PDFInfo
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Abstract
The invention provides a method for preparing plant protein/inorganic mineral nano-composite, wherein plant protein, inorganic mineral raw powder, reducing agent, plasticizer and coupling agent are dispersed or dissolved in water or acetic acid solution and stirred to react at low temperature, and the blend of plant protein/inorganic mineral is obtained by freeze-drying, and finally the plant protein /inorganic mineral nano-composite sheet or film is obtained with improved mechanical property, thermal property and barrier property by hot-press forming. The production method of the invention is simple and environment friendly, and the production cost is low.
Description
Technical field
The present invention relates to a kind of preparation method of renewable, biodegradable plant protein/inorganic mineral nano composite material, belong to natural agriculture polymer, protein chemistry, polymer chemistry, nano composite material, polymer shaping processing and biodegradable material field.
Background technology
In recent years, along with the growing tension of petroleum resources and also serious day by day, utilize natural polymer such as starch, protein, Mierocrystalline cellulose and chitin etc. to become one of international research hot of research and development for the raw material production bio-degradable plastics based on the problem of environmental pollution that synthesized polymer material caused of petrochemical complex.Vegetable-protein derives from agriculture renewable resources, as a kind of biopolymer, with the plastics fully biodegradable of its preparation, good mechanical performance, and has unique barrier, can be used for packaging field, and the application in other field also is foreseeable.
Protein is the important organic compound of a class, is prevalent in the organism by product of vegetable-protein and animal proteinum Chang Zuowei food-processing industry and can getting in a large number.Albumen is multipolymer, is made up of amino acid monomers different more than 20, is different from Polysaccharides, is made up of one or several monomer, resembles Mierocrystalline cellulose and starch is made up of glucose.Nonpolar (lipophilic), polarity non-ionic (hydrophilic) are arranged in the amino acid, pH=7 is positively charged and electronegative side group, the difference of these side groups and determine the amino acid (Cheftel etc. " amino acid in the food chemistry, peptide and protein " of different qualities, New York Marcel Dekker press published p245～369 in 1985).Most protein has 100～500 amino acid, protein one-level (elementary) structure according to amino acid collating sequence formation, determined the different structure (proteinic secondary structure) of protein along macromolecular chain, this secondary structure is based between the amino acid unit by Van der Waals (van der Waals) power, hydrogen bond, electrostatic force, lipophilicity and two sulfur-crosslinked interaction.Form its tertiary structure by the interaction of same type between proteinic secondary structure, form as ball, fibrous or random protein structure.The interphase interaction of final protein matter is unified into particular structure (quaternary structure) or biological activity.Albuminous membranae and coating are in forming process, can optimize proteinic configuration, protein interactions and proteinic film properties as heating, mechanical treatment, pressure, irradiation, bronsted lowry acids and bases bronsted lowry, metal ion by secondary, three grade and the quaternary structure of physics with the method modifying protein of chemistry.
Contain the protein about 10% in wheat, paddy and the corn grain, and in beans and some oil grain, protein content can be up to 30%-40%.When satisfying human growing demand, protein more function character is familiar with by people gradually, begins one's study to utilize plant protein production environment close friend's biodegradable plastic, especially for the material of food product pack at the exploitation protein resource." protein-based film and coating " book (Protein-Based Films andCoatings by the Gennadios chief editor, 2002 by CRC Press LLC.), comparatively the introduction of system utilize vegetable-proteins such as zein, gluten protein, soybean protein, cottonseed protein to prepare the method and the performance of edibility, degradable films or coating.The method for preparing the albumen plastics has two kinds, solution method and hot pressing formation process usually.Solution method is with protein, softening agent and some other auxiliary agent dissolvings or is to be dispersed in all kinds of SOLVENTS at least, casts then, sprays or flood, drying and moulding.This method need be dispersed in vegetable-protein in the aqueous solution or aqueous ethanolic solution of different acidity condition, utilize chemical reaction to destroy cystine linkage in the protein molecule to disperse and solubilized protein matter, be cast into very thin protein-based thin layer then, the final drying film forming.This method is the common method of vegetable-protein moulding, and studying the gluten protein film as people such as Pilar and Cuq is just (to see Journal ofAgricultural Food and Chemistry.2000,48:2954～2959 with this method casting film; 2003,51:7674～7654).United States Patent (USP) 5,965,708 disclose a kind of vegetable-protein base degradable without organic solvent, the preparation method of edible film, got with the preparation of continuous casting technology by the gluten protein of S-WAT reduction modification and the nothing alcohol aqueous dispersions that softening agent is formed, used aqueous phase system is in alkalescence (pH8～12).
Hot pressing formation process is that vegetable-protein becomes plastic material under the effect of heat and mechanical force, through cooling or removal volatile plasticizer form is fixed up again.Water and some other softening agent can reduce proteinic second-order transition temperature, it can be processed below causing the temperature of degraded, this means that also protein-based material can use the working method of traditional synthetic high polymer (as extrusion moulding, injection molding and compression molding etc.) and carry out machine-shaping.Solution method need consume a large amount of organic solvents and energy, also is not suitable for the moulding of big scale material.From Commercial Prospect, mold pressing or extruding-out process are faster more meaningful than the method for solution-casting film.
Protein has natural hydrophilic, also all be hydrophilic material usually for improving the softening agent that its processibility adds, so the resultant articles water tolerance is bad.Can improve the water resistance of product by modification or with the method for other material blend.As by chemically crosslinked, can improve the water tolerance of vegetable-protein film, also can utilize the barrier of the inorganic mineral of layered silicate to improve the water tolerance of albuminous membranae with the blend of grease, lipid acid.
With inorganic mineral and polymer blending, organic inorganic composite materials of formation has high intensity, modulus, thermotolerance, dimensional stability and barrier.And have the one dimension size at least in the nano inorganic mineral material of 1～100nm and the nano composite material of organic polymer formation, higher intensity, modulus, thermotolerance, dimensional stability and barrier are arranged.Meng Jiru, beam state are just waiting the research of the toughness reinforcing enhancing polymkeric substance of rigid particles have been carried out summing up (plastics, 2002,31 (2): 47～50), the inorganic mineral toughening polymer is the effect of stress concentration, can bring out the matrix surrender, absorb a large amount of deformation work, thereby produce toughening effect.But inorganic mineral powder is to be based upon on the basis of strict processing filler to the toughening effect of polymkeric substance, just need the surface of inorganic mineral powder is organised processing to improve the bonding of an organic inorganic interface, form the elasticity transition layer, effectively transmit and relaxed stress.Zhang Xu and Sun Fengjiu have carried out summing up (material Leader 2006 to the preparation of an organic inorganic nano composite material and the progress of performance, 20: 212～214), summarize in this matrix material that specific surface area is big, surface energy is high because nanoparticle has, its unique small-size effect is given many properties of nano composite material and function, for example excellent properties such as light, electricity, magnetic, heat and catalysis.
Polymkeric substance-laminated nm-silicate composite material research group of Japanese Toyota before 20 years has successfully prepared since nylon-6/ Nano composite material of montmorillonite, its high-modulus, intensity and stable on heating raising, barrier properties for gases and flame retardant properties etc., evoked the interest of industry and academia, extensive research has been carried out in this nano composite material preparation, structure, performance and application.Ray and Okamoto have carried out systematically summing up (Progressin Polymer Science, 2003,28:1539～1641) to the progress of polymkeric substance one stratiform silicate nanometer composite material.Yao Junyan and Yang Qingfang etc. have carried out summarizing (chemical propellant and macromolecular material to poly(lactic acid) (PLA), starch, polycaprolactone (PCL), Mierocrystalline cellulose, poly-hydroxyl alkane lipid acid (PHA), the shape silicate nanometer composite material preparation of polybutylene succinate biodegradable polymers basic units such as (PBS) and degradation property present Research and progress, 2007,5 (2): 40～44), layered silicate in the biodegradable polymers, the mechanical property of matrix material can be greatly improved, the degradation rate of material can be had influence on simultaneously.
U.S. Pat 2005008759 discloses the protein-based resin small-particle of being made up of protein hydrolysate and derivative thereof, deposit stable, applicable to injection moulding or extrusion moulding, preparation edible boilogical degraded goods.World patent WO2006134188 then invented a kind of by plant animal protein and 1～60% softening agent form through mold pressing and thermal treatment and biodegradable plastic, be applicable to wrapping material, system film and plastics.Gluten protein matter is the by product behind the wheat-flour separating starch, rival as a kind of agriculture polymer and other plant protein, people such as Day use to its development, preparation, modification, in foodstuffs industry and non-food product industry and have carried out summing up (Trends in Food Science and Technology, 2006,17 (2): 82～90).Gluten protein is as degradable, reproducible natural material, and its moderate cost with the bio-degradable plastics goods of its preparation, has solved resource and environmental protection problem based on the synthetic macromolecule of fossil oil.And can solve the easy situation of existing market, improve the production economic benefit of enterprise, more can improve peasant's kind grain enthusiasm and income.
The present invention prepares plant protein/inorganic mineral nano composite material by adding inorganic mineral, can improve the mechanical property and the thermostability of plant protein material, effectively improves the barrier of material.Press method of reducing commonly used in the protein chemistry, reductive agent (Cleland with the band sulfydryl, W.W., Biochemistry, 1964,3:480) open the cystine linkage of protein macromolecule, at high temperature, cystine linkage forms again, and molecular chain rearranges the more excellent cross-linked network structure of formation, has further improved the mechanical property of material.Add mercaptosilane coupling agents, can strengthen the interaction between inorganic mineral and the vegetable-protein, improve both the interface combinations and the mechanical property and the thermal characteristics of material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of plant protein/inorganic mineral nano composite material.Vegetable-protein is dispersed in the acidic aqueous solution that contains reductive agent, and low temperature obtains reductive vegetable-protein aqueous dispersions, or vegetable-protein at room temperature is dispersed in the acidic aqueous solution through stirring directly after stirring certain hour.In the vegetable-protein aqueous dispersions, add the softening agent and the former powder of inorganic mineral of organic modification not, add the coupling agent of need again; After stirring certain hour under the room temperature, through lyophilize Cheng Fenhou, available hot press forming technology is processed into the biodegradable plastics goods.Can prepare plant protein/inorganic mineral nano composite material with method of the present invention, inorganic mineral powder is dispersed on nanoscale in the vegetable-protein, and adding coupling agent can increase the biphase interface interaction, makes the mechanical property of material.Thermal characteristics and barrier property improve.
Basic composition is of plant protein/inorganic mineral nano composite material: vegetable-protein 100 weight parts, inorganic mineral 1～50 weight part, softening agent 0～40 weight part, reductive agent 0～2 weight part and coupling agent 0～2 weight part.
The concrete grammar of plant protein/inorganic mineral nano composite material preparation may further comprise the steps:
The reductive agent of (1) 0～2 weight part is dissolved in the aqueous solution of certain acidity, adds 100 weight part vegetable-proteins at low temperatures, stirring reaction 10～16h.Add 0～40 weight part softening agent and 1～50 weight part inorganic mineral again, stirring reaction 0.5～lh under the room temperature adds 0～2 weight part coupling agent, continues stirring reaction 0.5～1h, and lyophilize obtains plant protein/inorganic mineral blend powder;
(2) quantitative plant protein/inorganic mineral blend powder is placed mold cavity, with vulcanizing press, 120～160 ℃ molding temperature, the mold pressing pressure of 5～10MPa behind hot pressing 10～35min, takes out, be put in the chilling press rapidly, keep pressure at 5～10MPa, the 2～10min that colds pressing obtains plant protein/inorganic mineral nano composite plastic sheet or film.
Vegetable-protein among the present invention is gluten protein, zein, soybean protein, rice protein, Sunflower Receptacle albumen and cottonseed protein, can use wherein a kind of albumen, but also wherein any two or more albumen mix to use, and it is desirable to gluten protein; The former powder of inorganic mineral is polynite, attapulgite, kaolin, wilkinite, polygorskite, talcum, mica and lime carbonate, and the former powder of these inorganic minerals can use separately, but also two or more composite use it is desirable to polynite and attapulgite; Softening agent is glycerine, ethylene glycol, propylene glycol, Xylitol, sorbyl alcohol, oleic acid, stearic acid and lauric acid, and softening agent can use separately, but also two or more is used, and softening agent commonly used is a glycerine; Reductive agent is 1,4-dimercapto-2,3-butyleneglycol and halfcystine, can use separately or two kinds of composite uses, and the ideal reductive agent is 1,4-dimercapto-2,3-butyleneglycol (DTT); Coupling agent is γ-mercaptopropyl trimethoxysilane (A189) and gamma-mercaptopropyltriethoxysilane, can use separately or two kinds of composite uses.
The acidity of water is regulated by Glacial acetic acid among the present invention, and the pH scope of water is 3～7.Reduce in sour water under the vegetable-protein low temperature, reduction temperature is 2～6 ℃.Also can directly disperse without reduction at aqueous phase.The temperature of former powder of vegetable-protein or reducing powder and the former powder of inorganic mineral, softening agent and coupling agent blending dispersion is 4～40 ℃.It is 16～60 hours that the lyophilize of plant protein/inorganic mineral aqueous dispersions becomes the time of powder.In the plant protein/inorganic mineral powder mix, the inorganic mineral powder size has one dimension at least at 1～100nm.Plant protein/inorganic mineral nano composite material is processed with hot pressing formation process.
In the tensile property test of plant protein/inorganic mineral nano composite sheet, tensile bars standard reference ASTMD638TYPEV makes; Batten is done Elongation test (material tests company limited is newly thought carefully in Shenzhen for stretching experiment machine, CMT2203) at 25 ℃ behind the balance 48h under the RH=52.9% condition, draw speed is 1mm/min.
The rate of perviousness test reference standard ASTMD1653-93 of plant protein/inorganic mineral nano composite plastic film carries out.Test condition: 50 ℃ of temperature, 50%, 3 repetition of relative humidity, testing apparatus is 302A type temperature and humidity regulator (a Shanghai laboratory apparatus factory).
Advantage of the present invention is:
(1) the used vegetable-protein of the present invention be after reducing with inorganic mineral powder at acidity or neutral aqueous phase blended, do not contain alcohol, after lyophilize, in the hot-forming nano composite material, inorganic mineral is dispersed in the vegetable-protein at nanoscale, interface junction gets togather, and mechanical property, thermal characteristics and the barrier property of nano composite material are improved.
(2) the used inorganic mineral powder of the present invention is the former powder of inorganic mineral that need not organic modification, aqueous phase be with during cationic vegetable-protein mixes, realize mixing on the nanoscale by ion-exchange.A spot of coupling agent can effectively improve product performance.
(3) vegetable-protein derives from renewable agricultural resource, abundant raw material, moderate cost; The former powder wide material sources of inorganic mineral, raw material is easy to get, and can further reduce production costs; Plant protein/inorganic mineral nano composite material preparation technology is simple, easy handling; Plant protein/inorganic mineral nano composite membrane or sheet material fully biodegradable, compliance with environmental protection requirements.
Embodiment
Embodiment 1
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, add 1.00g glycerine, slowly add the 20.00g gluten protein, behind the powerful stirring 1h, add the 0.20g polynite, continue stirring reaction 0.5h, take out, lyophilize obtains gluten protein/polynite blend.Take by weighing quantitative blend in mould, under 140 ℃, at 6.5MPa precompressed 5min, boost to 10.0MPa again, hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/montmorillonite-based nano composite plastic sheet material, and tensile strength is 48MPa.
Embodiment 2
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, add 1.00g glycerine, slowly add the 20.00g gluten protein, behind the powerful stirring 1h, add the 1.00g polynite, continue stirring reaction 0.5h, take out, lyophilize obtains gluten protein/polynite blend.Take by weighing quantitative blend in mould, under 140 ℃, at 6.5MPa precompressed 5min, boost to 10.0MPa again, hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/montmorillonite-based nano composite plastic sheet material, and tensile strength is 55MPa.
Embodiment 3
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, add 1.00g glycerine, slowly add the 20.00g gluten protein, behind the powerful stirring 1h, add the 2.00g polynite, continue stirring reaction 0.5h, take out, lyophilize obtains gluten protein/polynite blend.Take by weighing quantitative blend in mould, under 140 ℃, at 6.5MPa precompressed 5min, boost to 10.0MPa again, hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/montmorillonite-based nano composite plastic sheet material, and tensile strength is 52MPa.
Embodiment 4
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, add 1.00g glycerine, slowly add the 20.00g gluten protein, powerful stir 1h after, take out, lyophilize obtains gluten protein/glycerine blend.Take by weighing quantitative blend in mould, under 140 ℃, 6.5MPa precompressed 5min boosts to 10.0MPa, and hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/glycerine composite plastic film, its rate of perviousness WVP (10
-3G.mm/m
2.d.kPa) be 618.
Embodiment 5
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, add 1.00g glycerine, slowly add the 20.00g gluten protein, behind the powerful stirring 1h, add the 2.00g polynite, continue stirring reaction 0.5h, take out, lyophilize obtains gluten protein/polynite blend.Take by weighing quantitative blend in mould, under 140 ℃, 6.5MPa precompressed 5min boosts to 10.0MPa, and hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/montmorillonite Composite plastics film, its rate of perviousness WVP (10
-3G.mm/m
2.d.kPa) be 369.
Embodiment 6
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, maintain the temperature at 4 ℃; Take by weighing 0.20gDTT and be dissolved in the acetum, slowly add the 20.00g gluten protein, stirring reaction 16h; Add 1.00g glycerine, 1.00g polynite, behind the stirring 0.5h, add 0.10g coupling agent A189 again, behind the continuation stirring reaction 0.5h, lyophilize obtains gluten protein/polynite blend.Take by weighing quantitative blend in mould, under 140 ℃, 6.5MPa precompressed 5min boosts to 10.0MPa, and hot pressing 15min takes out, and changes in chilling press and cools off, and obtains gluten protein/montmorillonite Composite plastics film, its rate of perviousness WVP (10
-3G.mm/m
2.d.kPa) be 474.
Embodiment 7
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, maintain the temperature at 4 ℃; Take by weighing 0.20gDTT and be dissolved in the acetum, slowly add the 20.00g gluten protein, stirring reaction spends the night; Add 1.00g glycerine, 1.40g attapulgite, behind the stirring 0.5h, add 0.10gA189 again, behind the continuation stirring reaction 0.5h, lyophilize obtains gluten protein/attapulgite blend.B. take by weighing quantitative blend in mould, in 130 ℃, 6.5 precompressed 5min under the MPa, pressure rises to 10.0MPa, hot pressing 25min, take out, be put in rapidly in the chilling press, keep pressure 10.0MPa, 5min colds pressing, obtain gluten protein/attapulgite clay nano composite plastic sheet, tensile strength is 58MPa.
Embodiment 8
Measure 200mL, acidity and be 4 acetum in the 500mL there-necked flask, maintain the temperature at 4 ℃; Take by weighing the 0.31g halfcystine and be dissolved in the acetum, slowly add the 20.00g soybean protein, stirring reaction 14h; Add 3.00g glycerine, 2.00g polynite, behind the stirring 0.5h, add 0.10gA189 again, behind the continuation stirring reaction 0.5h, lyophilize obtains soybean protein/polynite blend.Take by weighing quantitative blend in mould, precompressed 5min under 120 ℃, 6.5MPa, pressure rises to 10.0MPa, and hot pressing 15min takes out, and is put in rapidly in the chilling press, keeps pressure 10.0MPa, and the 5min that colds pressing obtains soybean protein/montmorillonite-based nano composite plastic sheet.
Claims (14)
1. the preparation method of a plant protein/inorganic mineral nano composite material is characterized in that being made up of the following step:
(1) be 3～7 at pH, the aqueous phase that contains reductive agent adds the vegetable-protein powder under stirring, and is stirred to and forms uniform dispersion liquid;
(2) in the aqueous dispersions of vegetable-protein, add softening agent, inorganic mineral powder and coupling agent under the stirring;
(3) vegetable-protein and inorganic mineral powder mixed dispersion liquid are dried to powder with cold method;
(4) with hot-press molding method suppress plant protein/inorganic mineral nano composite membrane or plate.
2. method according to claim 1 is characterized in that basic composition is of it: vegetable-protein 100 weight parts, inorganic mineral 1～50 weight part, reductive agent 0～2 weight part, softening agent 0～40 weight part and coupling agent 0～2 weight part.
3. according to the described method of claim 1, it is characterized in that described vegetable-protein is one or more combination of gluten protein, zein, soybean protein, rice protein, Semen arachidis hypogaeae protein, Sunflower Receptacle albumen and cottonseed protein.
4. method according to claim 1 is characterized in that, described inorganic mineral is the combination of one or more former powder of polynite, kaolin, wilkinite, talcum, mica, attapulgite and lime carbonate.
5. method according to claim 1 is characterized in that, described softening agent is glycerine, ethylene glycol, propylene glycol, Xylitol, sorbyl alcohol, oleic acid, stearic acid and lauric one or more combination.
6. method according to claim 1 is characterized in that, described reductive agent is 1,4-dimercapto-2, the combination of one or both of 3-butyleneglycol and halfcystine.
7. method according to claim 1 is characterized in that, described coupling agent is one or both the combination in γ-mercaptopropyl trimethoxysilane and the gamma-mercaptopropyltriethoxysilane.
8. method according to claim 1 is characterized in that the pH of water-dispersion is regulated by Glacial acetic acid.
9. method according to claim 1 is characterized in that, the aqueous phase system dispersion temperature is 1～40 ℃.
10. method according to claim 1 is characterized in that, the churning time of water dispersion system is 0.5～20h.
11. method according to claim 1 is characterized in that, vegetable-protein mixes at aqueous phase with the former powder of inorganic mineral after reducing, and also can directly mix at the former powder of aqueous phase and inorganic mineral without reduction.
12. method according to claim 1 is characterized in that, the plant protein/inorganic mineral aqueous dispersions is dried to powder mix with cryodesiccated method, and sublimation drying is 16～60 hours.
13. method according to claim 1 is characterized in that, in the plant protein/inorganic mineral powder mix, the size of inorganic mineral powder has one dimension at least between 1～100nm.
14. method according to claim 1, it is characterized in that, quantitative plant protein/inorganic mineral blend is added in the mold cavity, with vulcanizing press, 100～160 ℃ molding temperature, the mold pressing pressure of 5～10MPa behind hot pressing 10～60min, takes out, be put in the chilling press rapidly, keep pressure at 5～10MPa, the 2～30min that colds pressing obtains definite shape, biodegradable plant protein/inorganic mineral nano composite sheet or film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102643554A (en) * | 2012-05-08 | 2012-08-22 | 福州大学 | Edible fishskin collagen antibiosis membrane and preparing method thereof |
| CN103665895A (en) * | 2013-11-11 | 2014-03-26 | 青岛佰众化工技术有限公司 | Soybean protein isolate-polyaniline antimicrobial composite film |
| CN104017244A (en) * | 2014-01-08 | 2014-09-03 | 天津科技大学 | Montmorillonoid inserting layer nano composite membrane as well as preparation method and application thereof |
| CN104861662A (en) * | 2015-06-08 | 2015-08-26 | 四川大学 | Nano composite soy protein plastic and preparation method thereof |
| CN105694479A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Soybean protein biodegradable plastic |
| CN105694480A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Corn protein biodegradable plastics |
| CN105694481A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Wheat-protein biodegradable plastic |
| CN105713398A (en) * | 2015-09-18 | 2016-06-29 | 安徽柒柒塑业有限公司 | Sunflower protein biodegradable plastics |
| CN107936194A (en) * | 2017-11-20 | 2018-04-20 | 郑州源冉生物技术有限公司 | A kind of protein plastic of high intensity and its preparation method and application |
| WO2024007409A1 (en) * | 2022-07-07 | 2024-01-11 | 浙江升华云峰新材股份有限公司 | Modified-layered-silicate-basedaldehyde-free flame-retardant adhesive and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102643554A (en) * | 2012-05-08 | 2012-08-22 | 福州大学 | Edible fishskin collagen antibiosis membrane and preparing method thereof |
| CN102643554B (en) * | 2012-05-08 | 2013-12-04 | 福州大学 | Edible fishskin collagen antibiosis membrane and preparing method thereof |
| CN103665895A (en) * | 2013-11-11 | 2014-03-26 | 青岛佰众化工技术有限公司 | Soybean protein isolate-polyaniline antimicrobial composite film |
| CN104017244A (en) * | 2014-01-08 | 2014-09-03 | 天津科技大学 | Montmorillonoid inserting layer nano composite membrane as well as preparation method and application thereof |
| CN104017244B (en) * | 2014-01-08 | 2016-06-22 | 天津科技大学 | A kind of montmorillonite intercalation nano composite membrane and its preparation method and application |
| CN104861662A (en) * | 2015-06-08 | 2015-08-26 | 四川大学 | Nano composite soy protein plastic and preparation method thereof |
| CN105694479A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Soybean protein biodegradable plastic |
| CN105694480A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Corn protein biodegradable plastics |
| CN105694481A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Wheat-protein biodegradable plastic |
| CN105713398A (en) * | 2015-09-18 | 2016-06-29 | 安徽柒柒塑业有限公司 | Sunflower protein biodegradable plastics |
| CN107936194A (en) * | 2017-11-20 | 2018-04-20 | 郑州源冉生物技术有限公司 | A kind of protein plastic of high intensity and its preparation method and application |
| WO2024007409A1 (en) * | 2022-07-07 | 2024-01-11 | 浙江升华云峰新材股份有限公司 | Modified-layered-silicate-basedaldehyde-free flame-retardant adhesive and application thereof |
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