CN101092512A - Gluten powder / Nano silicon dioxide composite material in situ, and preparation method - Google Patents
Gluten powder / Nano silicon dioxide composite material in situ, and preparation method Download PDFInfo
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- CN101092512A CN101092512A CN 200710070112 CN200710070112A CN101092512A CN 101092512 A CN101092512 A CN 101092512A CN 200710070112 CN200710070112 CN 200710070112 CN 200710070112 A CN200710070112 A CN 200710070112A CN 101092512 A CN101092512 A CN 101092512A
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- Prior art keywords
- gluten powder
- composite material
- situ
- silicon dioxide
- nano silicon
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- 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.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 108010068370 Glutens Proteins 0.000 title claims description 41
- 235000021312 gluten Nutrition 0.000 title claims description 41
- 239000005543 nano-size silicon particle Substances 0.000 title claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011187 glycerol Nutrition 0.000 claims abstract description 12
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 21
- 102000004169 proteins and genes Human genes 0.000 abstract description 21
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 241000209140 Triticum Species 0.000 abstract description 10
- 235000021307 Triticum Nutrition 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract 6
- 229910052682 stishovite Inorganic materials 0.000 abstract 6
- 229910052905 tridymite Inorganic materials 0.000 abstract 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 235000018102 proteins Nutrition 0.000 description 13
- 108010073771 Soybean Proteins Proteins 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000019710 soybean protein Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940001941 soy protein Drugs 0.000 description 3
- 108010073032 Grain Proteins Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 101710159104 Flavor peptide Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 108010064851 Plant Proteins Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 238000009447 edible packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021118 plant-derived protein Nutrition 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001814 protein method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
This invention discloses a method for preparing wheat protein powder/nanoscale SiO2 in-situ composite material. The wheat protein powder/nanoscale SiO2 in-situ composite material comprises: wheat protein powder 100 parts, SiO2 nanoparticles 2-20 parts, and glycerin 5-43 parts. The method comprises: adding tetraethyl orthosilicate into ammonia solution of wheat protein powder, hydrolyzing to obtain SiO2 nanoparticles, adding glycerin plasticizer, drying, and mold-pressing to obtain wheat protein powder/nanoscale SiO2 in-situ composite material. The wheat protein powder/nanoscale SiO2 in-situ composite material has such advantages as wide wheat protein powder resources, simple preparation method, and no generation of toxic or harmful substances during preparation, and can be widely used in the field of degradable protein plastics and their composite materials.
Description
Technical field
The present invention relates to a kind of gluten powder/Nano silicon 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, prepare eco-friendly biodegradable plastic or edible packaging mould material with renewable, degradable plant resource as industrial chemicals, paid much attention in academia and industry member, become one of field, forward position of polymer material science and process engineering.Wheat preservation protein contains 40～50% prolamine and 35～45% gluten, has good film forming and plasticity-processing characteristics.The industrial goods of wheat preservation protein are gluten powder (protein content 70～85%), about 500,000 tons/year of global output, and 8.4 ten thousand yuan/ton of average prices, biodegradable plastic has development potentiality with new matrix material aspect.
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.The nano-particles filled modification is another approach that improves the protein material mechanical property.As Chinese patent application number 200610018534.2 " nanometer composite plastic with soya protein and preparation method thereof " the employing nano silicon is disclosed and soybean protein compound, improve the method for plastic of soybean protein mechanical property, soybean protein and silicon-dioxide are scattered in the water, in Banbury mixer, mix after the lyophilize, then compression molding with glycerine.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 aleuronat contains 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 matrix material.
Summary of the invention
The purpose of this invention is to provide a kind of gluten powder/Nano silicon dioxide composite material in situ and preparation method thereof.
Gluten powder/Nano silicon dioxide composite material in situ consist of gluten powder 100 weight parts, nano-silicon dioxide particle 2～20 weight parts, glycerine 5～43 weight parts.
The preparation method of gluten powder/Nano silicon dioxide composite material in situ: under agitation condition, at first tetraethoxy is joined weight percent concentration and be 5～10% gluten powder and weight percent concentration and be in the aqueous solution of 10～20% ammonia and react, temperature of reaction is 30～60 ℃, reaction times is 1～3h, tetraethoxy weight is 7～69% of gluten powder weight, add glycerine then, glycerine weight is 5～43% of gluten powder weight, be cast on the plastic plate, drying is 3～5 days under 30～60 ℃ of temperature, hot pressing 10～30min under 80～140 ℃ of temperature gets gluten powder/Nano silicon dioxide composite material in situ.
Advantage of the present invention is:
1) ammonia soln with gluten powder is a reaction medium, make tetraethoxy hydrolysis and generate nano-silicon dioxide particle under the catalysis of ammoniacal liquor, because the hydroxyl of silica particle surface is negative charge or slightly acidic, and there are static or interaction of hydrogen bond between the protein amido, protein molecule can be adsorbed onto silica particle surface, effectively suppress the reunion of silicon dioxide granule;
2) the teos hydrolysis by product is an ethanol, and ethanol and water can volatilize 30～60 ℃ of dryings, need not to remove especially.
Embodiment
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.
The present invention adopts the ammonia solvent grain protein, the protein soln of compounding high concentration; With gluten powder solution is reaction medium, drips the tetraethoxy ethanolic soln, and in-situ hydrolysis prepares the nano level nano-silicon dioxide particle, and generates ethanol byproducts.Ethanol and water can be removed 30～60 ℃ of dryings, are the volatilizations of accelerating alcohol and water with the purpose of solution casting on plastic plate.Glycerine can directly add in the solution.The direct compression molding of dried film can be obtained the gluten powder/Nano silicon dioxide composite material in situ of film like; Also dried film can be shredded, place mould to be pressed into difform goods.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
1) taking by weighing the 10g gluten powder, to add 90g concentration be in 10% the ammoniacal liquor, is made into protein concn and is 10% solution;
2) take by weighing the 10g tetraethoxy and add in the 90g dehydrated alcohol, be made into tetraethoxy concentration and be 10% solution;
3) under agitation condition, with 7g step 2) the gained teos solution adds in the step 1) gained gluten powder solution, at 60 ℃ of reaction 1h, adds 4.3g glycerine, with solution casting on polystyrene board 60 ℃ of dryings 3 days, gluten powder/nano silicon original position mixture;
4) step 3) gained film is shredded, places GB/T1040-92 plastic tensile performance test Standard Module, adopt vulcanizing press 140 ℃ with 5MPa pressure under hot pressing 10min, obtain gluten powder/Nano silicon dioxide composite material in situ after cooling, the demoulding.
Embodiment 2～5:
Concentration is that the consumption of 10% tetraethoxy ethanolic soln is respectively 14g, 21g, 28g, 35g, and all the other conditions are with embodiment 1.
Embodiment 6:
1) taking by weighing the 10g gluten powder, to add 90g concentration be in 20% the ammoniacal liquor, is made into protein concn and is 5% solution;
2) take by weighing the 6.9g tetraethoxy and add in the 27.6g dehydrated alcohol, be made into tetraethoxy concentration and be 20% solution;
3) under agitation condition, with step 2) the gained teos solution adds in the step 1) gained gluten powder solution, dropwises the back at 30 ℃ of reaction 3h, adds 0.5g glycerine, with solution casting on polyethylene board 30 ℃ of dryings 5 days, gluten powder/nano silicon original position mixture;
4) step 3) gained film is shredded adopt vulcanizing press 80 ℃ with 5MPa pressure under hot pressing 30min, the cooling back obtains gluten powder/Nano silicon dioxide composite material in situ.
The comparative example 1:
Adopt 7g ethanol to replace the 7g teos solution, all the other conditions are with embodiment 1.
Following table provides comparative example 1 and obtains water-intake rate and the mechanical property of gluten powder/Nano silicon dioxide composite material in situ when relative humidity 75% with embodiment 1～5 gained.
Gluten powder/nano silicon during table 1 relative humidity 75%
The water-intake rate of in-situ composite and mechanical property
| Dioxide-containing silica/% | Water-intake rate/% | Tensile strength/MPa | Elongation at break/% | Modulus/MPa | |
| The comparative example 1 | 0 | 22.4±0.5 | 3.5±0.1 | 154±12 | 21.8±1.6 |
| Embodiment 1 | 2 | 21.7±0.2 | 4.4±0.2 | 184±40 | 22.8±3.0 |
| Embodiment 2 | 4 | 21.3±0.3 | 4.3±0.3 | 161±19 | 25.6±2 |
| Embodiment 3 | 6 | 20.9±0.1 | 4.3±0.2 | 168±18 | 25.7±0.5 |
| Embodiment 4 | 8 | 19.8±0.3 | 6.7±0.4 | 138±11 | 49.3±4.2 |
| Embodiment 5 | 10 | 1 8.8±0.2 | 5.9±0.1 | 76±21 | 55.2±7.8 |
The invention provides a kind of gluten powder/Nano silicon dioxide composite material in situ and preparation method thereof.Main raw material gluten powder involved in the present invention belongs to renewable agricultural resource, and is for wheat starch industrial processes byproduct, cheap; The preparation method and the technical process of gluten powder/Nano silicon dioxide composite material in situ involved in the present invention are simple, are easy to promotion and implementation.
Claims (2)
1. a gluten powder/Nano silicon dioxide composite material in situ is characterized in that, it consist of gluten powder 100 weight parts, nano-silicon dioxide particle 2～20 weight parts, glycerine 5～43 weight parts.
2. the preparation method of a gluten powder/Nano silicon dioxide composite material in situ as claimed in claim 1, it is characterized in that, under agitation condition, at first tetraethoxy is joined weight percent concentration and be 5～10% gluten powder and weight percent concentration and be in the aqueous solution of 10～20% ammonia and react, temperature of reaction is 30～60 ℃, reaction times is 1～3h, tetraethoxy weight is 7～69% of gluten powder weight, add glycerine then, glycerine weight is 5～43% of gluten powder weight, be cast on the plastic plate, drying is 3～5 days under 30～60 ℃ of temperature, hot pressing 10～30min under 80～140 ℃ of temperature gets gluten powder/Nano silicon dioxide composite material in situ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100701124A CN100532461C (en) | 2007-07-20 | 2007-07-20 | Gluten powder / nano silicon dioxide in situ composite material, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100701124A CN100532461C (en) | 2007-07-20 | 2007-07-20 | Gluten powder / nano silicon dioxide in situ composite material, and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101092512A true CN101092512A (en) | 2007-12-26 |
| CN100532461C CN100532461C (en) | 2009-08-26 |
Family
ID=38990958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100701124A Expired - Fee Related CN100532461C (en) | 2007-07-20 | 2007-07-20 | Gluten powder / nano silicon dioxide in situ composite material, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100532461C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602861B (en) * | 2009-07-07 | 2012-03-28 | 河南工业大学 | Method for preparing silica modified wheat gluten protein nano-composite material |
| CN106137994A (en) * | 2016-08-18 | 2016-11-23 | 成都新柯力化工科技有限公司 | A kind of stable tablet of clopidogrel and preparation method thereof |
-
2007
- 2007-07-20 CN CNB2007100701124A patent/CN100532461C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602861B (en) * | 2009-07-07 | 2012-03-28 | 河南工业大学 | Method for preparing silica modified wheat gluten protein nano-composite material |
| CN106137994A (en) * | 2016-08-18 | 2016-11-23 | 成都新柯力化工科技有限公司 | A kind of stable tablet of clopidogrel and preparation method thereof |
| CN106137994B (en) * | 2016-08-18 | 2018-11-09 | 成都新柯力化工科技有限公司 | A kind of stable tablet of clopidogrel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100532461C (en) | 2009-08-26 |
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Granted publication date: 20090826 Termination date: 20120720 |