CN100540608C - Grain protein/Nano particle composite material in situ and preparation method thereof - Google Patents
Grain protein/Nano particle composite material in situ and preparation method thereof Download PDFInfo
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- CN100540608C CN100540608C CNB2007100701251A CN200710070125A CN100540608C CN 100540608 C CN100540608 C CN 100540608C CN B2007100701251 A CNB2007100701251 A CN B2007100701251A CN 200710070125 A CN200710070125 A CN 200710070125A CN 100540608 C CN100540608 C CN 100540608C
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Abstract
The invention discloses grain protein/Nano particle composite material in situ and preparation method thereof.Grain protein/Nano particle composite material in situ comprises grain protein 100 weight parts, nanoparticle 10～100 weight parts, softening agent 10～100 weight parts.Its preparation method is, in the ammonia soln of grain protein, add magnesium chloride or aluminum chloride, hydrolysis produces nano-sized magnesium hydroxide or aluminum hydroxyl nano particle, washing, dry back add softening agent, obtain grain protein/nanoparticle original position mixture, the matrix material that adopts the compression molding preparation to have excellent mechanical property.Main raw material grain protein involved in the present invention belongs to renewable agricultural resource, wide material sources; The preparation method and the technical process of grain protein/Nano particle composite material in situ involved in the present invention are simple, and low production cost is easy to promotion and implementation.
Description
Technical field
The present invention relates to a kind of grain protein/Nano particle composite material in situ and preparation method thereof.
Background technology
Our times plastics ultimate production surpasses 1.7 hundred million tons, has been penetrated into the every field of national economy all departments and people's lives.Serious day by day along with the in short supply day by day of petroleum resources and environmental pollution that synthesized polymer material caused, with renewable, degradable plant resource as industrial chemicals, more and more paid much attention to, become one of field, forward position of polymer material science and process engineering.
Corn protein is the byproduct of starch industry, and is main at present as fodder additives, and part is used for food improver or produces flavor peptides, amino acid.Adopting corn protein to prepare degradable plastics is one of effective way that improves its added value, alleviation white pollution.The mechanical property of corn protein plastics is relatively poor, needs to wait rigidity, thermotolerance and the water tolerance that improves material through uv irradiation, gamma-radiation irradiation, enzyme processing or chemically crosslinked.Chinese patent application number 200610018518.3 " soy-protein/aluminium hydrate nano composite materials and its production and use " disclose the employing nano-aluminum hydroxide and have improved soybean protein material intensity and inflexible method, soy-protein is scattered in the aluminum chloride aqueous solution, adopt ammoniacal liquor and aluminium reaction to form the gel mixture, obtain to extrude the soy-protein/aluminium hydrate nano mixture of processing after drying.Yet grain protein such as aleuronat contain the gluten of toughness prolamine and heavy molecular weight, in case aquation promptly forms the dough of high viscosity, even also be difficult to form stable suspension liquid of protein under the lower situation of concentration.Thereby, when adopting suspension method to prepare the grain protein nano composite material, be difficult to guarantee the homodisperse of nanoparticle in mixture.
Summary of the invention
The purpose of this invention is to provide a kind of grain protein/Nano particle composite material in situ and preparation method thereof.
Consisting of of grain protein/Nano particle composite material in situ: grain protein 100 weight parts, nanoparticle 10～100 weight parts, softening agent 10～100 weight parts.
The preparation method of grain protein/Nano particle composite material in situ: at first grain protein is joined weight percent concentration and be in 10～25% the ammoniacal liquor, be made into weight percent concentration and be 5～20% grain protein solution, under agitation condition, drip weight percent concentration then and be 10～40% aqueous chloride solution, reaction 0.5～1h, transfer pH to 6～7, centrifugation, lower floor's slurries are with deionized water wash and centrifugation, repeat 5～8 times, dry, ground 100 mesh sieves, add softening agent again, softening agent weight is 10～100% of grain protein weight, place mould, mold pressing 10～30min under 100～140 ℃ of temperature obtains grain protein/Nano particle composite material in situ goods.
Described grain protein is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin.Nanoparticle is nano-sized magnesium hydroxide particle or nano-aluminum hydroxide particle.Nanoparticle is that in-situ hydrolysis produced metal chloride in the aqueous solution of grain protein.Softening agent is glycol ether, triglycol, 1,4-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, glycerine, 1,2,4-trihydroxybutane, 1,2,3-hexanetriol or 1,2,6-hexanetriol.Metal chloride is magnesium chloride or aluminum chloride.
Advantage of the present invention is:
1) adopting the ammonia solution of grain protein is reaction medium, make magnesium chloride or aluminum chloride hydrolysis generate magnesium hydroxide or aluminum hydroxyl nano particle, its surface hydroxyl can form hydrogen bond action with amido on the protein molecule chain, carboxyl etc., thereby suppresses the reunion of nanoparticle;
2) residual amino molecule can volatilize in drying or mold process voluntarily after the muriate hydrolysis, does not need special removal;
3) grain protein/Nano particle composite material in situ has excellent moulding processability, can adopt compression molding to prepare composite product;
4) safety non-toxic of grain protein/Nano particle composite material in situ has biodegradation character.
Embodiment
The preparation of grain protein/nanoparticle original position mixture is a key of the present invention.The present invention adopts alkaline solution to dissolve grain protein first, and the protein soln of compounding high concentration drips magnesium chloride or liquor alumini chloridi, and in-situ hydrolysis generates magnesium hydroxide or aluminum hydroxyl nano particle.Form dispersion liquid or suspension if grain protein does not dissolve, nanoparticle disperses inhomogeneous in solution and occurs reuniting.In magnesium chloride or aluminum chloride hydrolytic process, should stir incessantly, to promote the homodisperse of nanoparticle in protein soln.Can add an amount of softening agent in the solution after hydrolysis is finished, and it is uniformly dispersed when stirring, and obtains grain protein/nanoparticle original position mixture after 50～80 ℃ of dryings are removed moisture.
Above-mentioned grain protein/nanoparticle original position mixture can adopt the conventional direct compression molding of vulcanizing press, and molding temperature is advisable with 100～140 ℃.In this temperature range, protein molecule forms network structure by intermolecular disulfide bond.
Grain protein/Nano particle composite material in situ that the present invention obtained is implemented crosslinked by disulfide linkage between protein molecule.Under field conditions (factors), these disulfide linkage can rupture, and protein molecule can be hydrolyzed to amino acid.Thereby the grain protein/Nano particle composite material in situ that is obtained can be degraded fully, and its resistates magnesium hydroxide or aluminium hydroxide are harmless fully to environment.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
Taking by weighing the 2g gluten powder, to add 18g concentration be in 12% the ammoniacal liquor, be made into protein concn and be 10% solution, dropping 1.3g concentration is 28% magnesium chloride brine under agitation condition, dropwise the back and continue reaction 0.5h, transfer pH to 6, centrifugation, lower floor's slurries are with deionized water wash and centrifugation, repeat 5 times, dry, ground 100 mesh sieves, obtain grain protein/nano-particle compound, add 1g glycerine, stir, place GB/T1040-92 plastic tensile performance test Standard Module, at 120 ℃ of hot pressing 20min, obtain grain protein/Nano particle composite material in situ goods, its protein/magnesium hydroxide/softening agent ratio is 100/10/50.
Embodiment 2～5:
Concentration is that the dripping quantity of 28% magnesium chloride brine is respectively 2.9g, 5.0g, 7.8g, 11.7g, all the other conditions are with embodiment 1, and the protein/magnesium hydroxide in grain protein/Nano particle composite material in situ that obtains/softening agent ratio is respectively 100/10/50,100/25/50,100/43/50,100/67/50,100/100/50.
Embodiment 6:
Taking by weighing the 10g rice protein powder, to add 190g concentration be in 10% the ammoniacal liquor, be made into protein concn and be 5% solution, dropping 100g concentration is 10% aluminum chloride aqueous solution under agitation condition, dropwise the back and continue reaction 1h, transfer pH to 7, centrifugation, lower floor's slurries repeat drying 8 times with deionized water wash and centrifugation, ground 100 mesh sieves, obtain grain protein/nano-particle compound, add the 1g glycol ether, stir, place GB/T1040-92 plastic tensile performance test Standard Module, at 140 ℃ of hot pressing 10min, obtain grain protein/Nano particle composite material in situ goods.
Embodiment 7:
Taking by weighing the 10g wheat gliadin, to add 40g concentration be in 25% the ammoniacal liquor, be made into protein concn and be 20% solution, dropping 19.5g concentration is 40% aluminum chloride aqueous solution under agitation condition, dropwise the back and continue reaction 1h, transfer pH to 6.5, centrifugation, lower floor's slurries repeat drying 6 times with deionized water wash and centrifugation, ground 100 mesh sieves, get gluten powder/nanoparticle original position mixture, add the 10g triglycol, stir, place GB/T1040-92 plastic tensile performance test Standard Module, at 100 ℃ of hot pressing 30min, obtain grain protein/Nano particle composite material in situ goods.
Embodiment 8～10:
Replace gluten powder with hordein, zein or kafirin respectively, all the other conditions are with embodiment 1.
Embodiment 11～18:
Respectively with 1,4-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 1,2,4-trihydroxybutane, 1,2,3-hexanetriol or 1,2, the 6-hexanetriol replaces glycol ether, and all the other conditions are with embodiment 6.
The invention provides a kind of grain protein/Nano particle composite material in situ and preparation method thereof.Main raw material grain protein involved in the present invention belongs to renewable agricultural resource, wide material sources; The preparation method and the technical process of grain protein/Nano particle composite material in situ involved in the present invention are simple, and low production cost is easy to promotion and implementation.Grain protein/the Nano particle composite material in situ that makes based on the present invention has excellent mechanics, and protein can be degraded its residue magnesium hydroxide or aluminium hydroxide environmental sound under field conditions (factors) fully.
Claims (3)
1. grain protein/Nano particle composite material in situ, it is characterized in that, consisting of of it: grain protein 100 weight parts, nanoparticle 10～100 weight parts, softening agent 10～100 weight parts, described grain protein is a gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin, nanoparticle is nano-sized magnesium hydroxide particle or nano-aluminum hydroxide particle, softening agent is a glycol ether, triglycol, 1, the 4-butyleneglycol, 1,3 butylene glycol, 2, the 3-butyleneglycol, glycerine, 1,2, the 4-trihydroxybutane, 1,2, the 3-hexanetriol, or 1,2, the 6-hexanetriol.
2. grain protein/Nano particle composite material in situ according to claim 1, it is characterized in that, described nanoparticle be metal chloride in-situ hydrolysis produced in the aqueous solution of grain protein, described metal chloride is magnesium chloride or aluminum chloride.
3. the preparation method of a grain protein/Nano particle composite material in situ as claimed in claim 1, it is characterized in that, at first grain protein is joined weight percent concentration and be in 10～25% the ammoniacal liquor, be made into weight percent concentration and be 5～20% grain protein solution, under agitation condition, drip weight percent concentration then and be 10～40% the metal chloride aqueous solution, reaction 0.5～1h, transfer pH to 6～7, centrifugation, lower floor's slurries are with deionized water wash and centrifugation, repeat 5～8 times, dry, ground 100 mesh sieves, add softening agent again, softening agent weight is 10～100% of grain protein weight, the mixture that adds softening agent is placed mould, mold pressing 10～30min under 100～140 ℃ of temperature, obtain grain protein/Nano particle composite material in situ goods, described grain protein is a gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin, softening agent is a glycol ether, triglycol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 2, the 3-butyleneglycol, glycerine, 1,2, the 4-trihydroxybutane, 1,2, the 3-hexanetriol, or 1,2,6-hexanetriol, metal chloride are magnesium chloride or aluminum chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100701251A CN100540608C (en) | 2007-07-20 | 2007-07-20 | Grain protein/Nano particle composite material in situ and preparation method thereof |
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| CNB2007100701251A CN100540608C (en) | 2007-07-20 | 2007-07-20 | Grain protein/Nano particle composite material in situ and preparation method thereof |
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| CN101092514A CN101092514A (en) | 2007-12-26 |
| CN100540608C true CN100540608C (en) | 2009-09-16 |
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| CNB2007100701251A Expired - Fee Related CN100540608C (en) | 2007-07-20 | 2007-07-20 | Grain protein/Nano particle composite material in situ and preparation method thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012007628A1 (en) * | 2010-07-16 | 2012-01-19 | Instituto Científico Y Tecnológico De Navarra, S.A. | Nanoparticles for encapsulation of compounds, the production and uses thereof |
| CN103214858A (en) * | 2013-04-16 | 2013-07-24 | 惠州市诺亚维纳米环保材料有限公司 | Soybean protein nanocomposite test piece as well as preparation method and application of test piece |
| CN109676149B (en) * | 2018-12-13 | 2020-12-22 | 华南理工大学 | Green synthetic wheat gliadin/nano-silver particle with core-shell structure and preparation method and application thereof |
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