CN101092515A - Protein in grain / Nano titanium dioxide composite material in situ, and preparation method - Google Patents

Protein in grain / Nano titanium dioxide composite material in situ, and preparation method Download PDF

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Publication number
CN101092515A
CN101092515A CN 200710070128 CN200710070128A CN101092515A CN 101092515 A CN101092515 A CN 101092515A CN 200710070128 CN200710070128 CN 200710070128 CN 200710070128 A CN200710070128 A CN 200710070128A CN 101092515 A CN101092515 A CN 101092515A
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protein
composite material
grain protein
titanium dioxide
grain
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CN 200710070128
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CN100519661C (en
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宋义虎
郑强
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

This invention discloses a method for preparing cereal proteins/nanoscale TiO2 composite material. The cereal proteins/nanoscale TiO2 composite material comprises: cereal proteins 100 parts, nanoscale TiO2 5-20 parts, and plasticizer 5-30 parts. The method comprises: adding TiO2 nanoparticles and glycerin into ammonia solution of cereal proteins, stirring so that TiO2 nanoparticles are uniformly dispersed, concentrating, drying to remove water and obtain cereal proteins/nanoscale TiO2 composite, and molding at 100-140 deg.C to obtain cereal proteins/nanoscale TiO2 composite material. The cereal proteins/nanoscale TiO2 composite material has such advantages as wide cereal protein resources, simple preparation method and low cost, and can be widely used in degradable protein plastic field.

Description

Grain protein/Nano titanium dioxide composite material in situ and preparation method thereof
Technical field
The present invention relates to a kind of grain protein/Nano titanium dioxide 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 glue 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 preparation method who the purpose of this invention is to provide a kind of grain protein/Nano titanium dioxide composite material in situ.
The preparation method of grain protein/nanometer titanium dioxide composite material: at first grain protein is joined weight percent concentration and be in 10~20% the ammoniacal liquor, be made into weight percent concentration and be 5~10% grain protein solution, add nano-titania particle then, nano titanium oxide weight is 5~20% of grain protein weight, add softening agent again, softening agent weight is 5~30% of grain protein weight, stirring makes the nano-titania particle homodisperse, dry under 50~80 ℃ of temperature, compression molding under 100~140 ℃ of temperature, clamp time is 10~30min, obtains grain protein/nanometer titanium dioxide composite material.
Described grain protein is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin.Softening agent is glycerine or trolamine.The particle diameter of nano-titania particle is that 5~30nm, specific surface area are 40~400m 2/ g.
Advantage of the present invention is: the ammonia soln with grain protein is that medium prepares stabilized nano TiO 2 particles suspension, and the physics that strengthens between protein and TiO 2 particles interacts, and improves the mechanical strength of protein material.
Embodiment
It is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin that the present invention uses protein.
Gluten powder also claims vital wheat gluten, is a kind of natural plant protein matter of extracting for the raw material deep processing with the whole meal flour.Suitable gluten powder can be selected from the commerical prod of protein content 〉=75% (butt), buys gluten powder as can be from Shanghai prosperous flavor Food Co., Ltd, Zhoukou City's "Lotus" gourmet powder group, sky, Henan Province hat vegetable-protein company limited, the happy health food in Tongcheng City, Anhui Province company limited.
Rice protein powder is a kind of highly purified rice protein product of producing from rice meal, rice slag or rice are poor, its protein content 〉=80% (butt).The technology of extracting rice protein from rice meal, rice slag or rice are poor is known, as stating in following document, the document is incorporated herein by reference: " Wang Zhangcun, Yao Huiyuan: Extraction of Rice Protein from Rice Dregs. research grain and fodder industry; 2003, (8): 37-38 ".In addition, Chinese patent 03 134973.0 discloses " extracting the method for rice protein from rice ", Chinese patent 03134972.2 discloses " alkaline process extracts the method for rice protein ", and Chinese patent 200410039303.0 discloses " being raw material extraction rice protein and the processing method of making Starch rice with the rice ".Suitable rice protein powder also can be selected from the commerical prod of protein content 〉=80% (butt), as buying rice protein powder from Guilin Red Star bio tech ltd.
The technology of extracting wheat gliadin from wheat-flour is known, as in following document, stating, the document is incorporated herein by reference: " sesame is learned by department; Li Jianwei; Wang Jinshui, girth intelligence, the research of gliadine and glutenin extraction conditions. Zhengzhou Engineering College's journal; 2004,25 (3): 33-39 ".
The technology of extracting hordein from barley grain or seed powder is known, as in following document, stating, these documents are incorporated herein by reference: " Yan Qichuan; yellow second place; Xu Yuan; the seeds prolamine electrophoresis method that ISTA on probation recommends is identified barley and wheat breed. Acta Agronomica Sinica, 1992,18 (1): 61-68; The Dong ox, Wang Lirong, Lan Lan, Zhang Deyi, the dissolution characteristics of high-lysine component research in the hordein. the plant department of the Chinese Academy of Sciences, 1989,31:689-695 ".
The technology of extracting zein from Zein powder (also claiming corn gluten meal) is known, as in following document, stating, the document is incorporated herein by reference: " Zhang Zhong; Qi Aiyun: zein extraction process and Study on Functional; grain and fodder industry; 2004 (9): 21-23. " Chinese patent 00101222.3 discloses the technology of " using preparing alcohol-soluble corn protein membrane from corn gluten ", has wherein described the method for extracting zein from Zein powder.Highly purified zein can be selected from the commerical prod of protein content 〉=80% (butt), can buy zein from Japan and the pure medicine of light company, U.S. Freeman Industries company.
The technology of extracting kafirin from sorghum seed or sorghum flour is known, as in following document, stating, these documents are incorporated herein by reference: " Emmambux MN.; Taylor JRN.; Sorghumkafirin interaction with various phenolic compounds.J.Sci.Food Agric.; 2003,83:402-407; Gao C., Taylor J., Wellner N., Byaruhanga YB., Parker ML., Mills ENC., Belton PS., Effect of preparation conditions on protein secondary structure andbiofilm formation of Kafirin.J.Agric.Food Chem., 2005,53:306-3 12; Huang CP., Hejlsoe-Kohsel E., Han XZ., Protelytic activity in sorghum flour and its interferencein protein analysis.Cereal Chem., 2000,77:343-344 ".
The present invention adopts the ammonia solvent grain protein, and the protein soln of compounding high concentration is suspended in nano-titania particle in the protein soln then.Owing to exist physical chemistry to interact the difficult reunion of TiO 2 particles in protein soln between protein active group and titanium dioxide.Softening agent glycerine can directly add in the solution, and drying dewaters then.In drying process, protein and TiO 2 particles co-precipitation form stable grain protein/nano titanium oxide mixture.With mixture with the exsiccant film 100~140 ℃ of compression moldings, can improve the protein cross degree, improve the mechanical strength of matrix material, and remove residual ammonia.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
Taking by weighing 10g gluten powder (Shanghai prosperous flavor Food Co., Ltd product), to add 90g concentration be in 10% the ammoniacal liquor, be made into protein concn and be 10% solution, add 2g anatase-type nanometer titanium dioxide (sky, Wuhan excitability rice photocatalyst material company limited product, median size 30nm, specific surface area 40m 2/ g) with 0.5g glycerine, induction stirring 30min makes TiO 2 particles and glycerine homodisperse, removed moisture in 3 days 50 ℃ of dryings, grain protein/nano titanium oxide mixture obtains grain protein/nanometer titanium dioxide composite material in 100 ℃ of mold pressing 30min moulding.The electronic tensile machine test result shows that the tensile strength of grain protein/nanometer titanium dioxide composite material is 16 ± 1.2MPa, and elongation at break is 54 ± 2%.
Embodiment 2:
Taking by weighing 20g rice protein powder (the rich biochemical product in Hangzhou three company limited product), to add 380g concentration be in 20% the ammoniacal liquor, be made into protein concn and be 5% solution, add 1g rutile type nano titanic oxide (Hangzhou ten thousand scape novel material company limited products, median size 5nm, specific surface area 400m 2/ g) with the 6g trolamine, induction stirring 30min makes TiO 2 particles and glycerine homodisperse, removed moisture in 3 days 80 ℃ of dryings, grain protein/nano titanium oxide mixture obtains grain protein/nanometer titanium dioxide composite material in 140 ℃ of mold pressing 10min moulding.The electronic tensile machine test result shows that the tensile strength of grain protein/nanometer titanium dioxide composite material is 6 ± 0.8MPa, and elongation at break is 114 ± 8%.
Embodiment 3~6:
Replace gluten powder with wheat gliadin, hordein, zein or kafirin respectively, all the other conditions are with embodiment 1.
The invention provides a kind of grain protein/nanometer titanium dioxide composite material 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/nanometer titanium dioxide composite material involved in the present invention are simple, and low production cost is easy to promotion and implementation.

Claims (4)

1. the preparation method of a grain protein/nanometer titanium dioxide composite material, it is characterized in that, at first grain protein is joined weight percent concentration and be in 10~20% the ammoniacal liquor, be made into weight percent concentration and be 5~10% grain protein solution, add nano-titania particle then, nano titanium oxide weight is 5~20% of grain protein weight, add softening agent again, softening agent weight is 5~30% of grain protein weight, stirring makes the nano-titania particle homodisperse, dry under 50~80 ℃ of temperature, compression molding under 100~140 ℃ of temperature, clamp time is 10~30min, obtains grain protein/nanometer titanium dioxide composite material.
2. the preparation method of grain protein/nanometer titanium dioxide composite material according to claim 1, it is characterized in that described grain protein is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin.
3. the preparation method of grain protein/nanometer titanium dioxide composite material according to claim 1 is characterized in that, described softening agent is glycerine or trolamine.
4. grain protein/nanometer titanium dioxide composite material according to claim 1 is characterized in that, the particle diameter of described nano-titania particle is that 5~30nm, specific surface area are 40~400m 2/ g.
CNB2007100701285A 2007-07-20 2007-07-20 Protein in grain / Nano titanium dioxide composite material in situ, and preparation method Expired - Fee Related CN100519661C (en)

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CN100519661C CN100519661C (en) 2009-07-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504549A (en) * 2011-09-28 2012-06-20 福州大学 Titanium dioxide-soy protein isolate composite nano antimicrobial film and preparation method thereof
CN103666254A (en) * 2013-12-10 2014-03-26 上海理工大学 Film-forming solution, and preparation method and application thereof
CN109676149A (en) * 2018-12-13 2019-04-26 华南理工大学 A kind of wheat gliadin/nano-Ag particles of green syt core-shell structure and the preparation method and application thereof
CN112552693A (en) * 2020-12-18 2021-03-26 山东大学 Zein/titanium dioxide composite membrane and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504549A (en) * 2011-09-28 2012-06-20 福州大学 Titanium dioxide-soy protein isolate composite nano antimicrobial film and preparation method thereof
CN102504549B (en) * 2011-09-28 2013-10-30 福州大学 Titanium dioxide-soy protein isolate composite nano antimicrobial film and preparation method thereof
CN103666254A (en) * 2013-12-10 2014-03-26 上海理工大学 Film-forming solution, and preparation method and application thereof
CN103666254B (en) * 2013-12-10 2015-12-30 上海理工大学 A kind of film forming liquid, preparation method and application thereof
CN109676149A (en) * 2018-12-13 2019-04-26 华南理工大学 A kind of wheat gliadin/nano-Ag particles of green syt core-shell structure and the preparation method and application thereof
CN112552693A (en) * 2020-12-18 2021-03-26 山东大学 Zein/titanium dioxide composite membrane and preparation method and application thereof
CN112552693B (en) * 2020-12-18 2022-03-15 山东大学 Zein/titanium dioxide composite membrane and preparation method and application thereof

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