CN1740232A - Degradable plastic with cross-linked N-acylated grain protein and its prepn process - Google Patents
Degradable plastic with cross-linked N-acylated grain protein and its prepn process Download PDFInfo
- Publication number
- CN1740232A CN1740232A CN 200510060499 CN200510060499A CN1740232A CN 1740232 A CN1740232 A CN 1740232A CN 200510060499 CN200510060499 CN 200510060499 CN 200510060499 A CN200510060499 A CN 200510060499A CN 1740232 A CN1740232 A CN 1740232A
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- Prior art keywords
- acylated
- grain protein
- cross
- protein
- acid
- Prior art date
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Landscapes
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Abstract
The degradable cross-linked N-acylated grain protein plastic includes N-acylated grain protein 100 weight portions, plasticizer 20-100 weight portions, lubricant 0.5-1.5 weight portions, antioxidant 0.5-1.5 weight portions, preservative 0.1-1 weight portions and cross-linking agent 1-7 weight portions. The preparation process includes N-acylating modification of grain protein with acyl chloride or acid anhydride with double bond to introduce side chain with double bond to grain protein molecule; matching N-acylated grain protein with non-toxic plasticizer, lubricant, antioxidant, preservative and cross-linking agent; thermoplastic processing and high temperature molding to obtain the degradable cross-linked N-acylated grain protein plastic with excellent waterproof and antiageing performance.
Description
Technical field
The present invention relates to a kind of cross-linking type N-acylated grain protein degradable plastics 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 and people's lives.Yet plastic raw materials is subjected to the restriction of oil shortage to show especially out day by day, and the environmental pollution that the discarded back of a large amount of plastics is caused is serious day by day.According to statistics, waste plastic accounts for 7～8% of developed country's rubbish total amount.The development degradable plastics can reduce white pollution, and the economy and society benefit that highlights is arranged.With natural polymers such as agricultural-food natural polymer such as starch, Mierocrystalline cellulose, chitin, protein is the raw material production degradable plastics, becomes one of international research hot of research and development.The exploitation comparative maturity of full starch-type degradable plastics, is main raw material as U.S. Wamer-Lambert company, SUMITOMO CHEMICAL Itochu, Italian Ferruzzi company with starch based agricultural-food such as corn, potato or sweet potatoes, make the complete biodegradable plastic (Chen Yun who contains 90% above starch, explain the literary composition that continues, Qiu Xianhua, Wang Feidi, Qiu Weiyang, starch plastic present situation and development prospect. polymer circular, 2000, (4): 77-82).
Have a long history for the feedstock production plastics with the plant protein, all delivered patent (the Edekson DR. for preparing half plastics by soy-protein as France and Britain in 1913, Practical handbook ofsoybean processing and utillization.St.L.Missouri:AOCS Press and UnitedSoybean Board, 1993,387-391).After the forties in 20th century, along with the rise of petrochemical industry, synthetic plastics has been controlled market, and people seldom study proteinic plasticity-processing.In recent years, for reasons such as environment protection and petrochemical industry shortages of resources, people begin to restudy the biodegradable plastic that utilizes plant protein production environment close friend, the food product pack mould material that particularly consumption is huge.Gennadios etc. have commented based on the edible film of gluten powder, soybean protein, zein, milk proteins, Semen arachidis hypogaeae protein or collagen protein etc. or the preparation method and performance (the Gennadios A. of coated material, McHugh TH., Weller CL., KrochtaJM., Edible coatings and films based on proteins.In Edible coatings and films toimprove food quality; Krochta JM., Baldwin EA., Nisperos-Carriedo MO., Eds., Technomic Publishing Co.:Lancaster, PA, 1994; 201-277).
The natural polymer that protein is made up of multiple amino acids, the interaction of hydrogen bond that intermolecular existence is stronger and intramolecularly/intermolecular disulfide bond.Usually solution or the suspension with protein, softening agent and other reagent is filming medium, adopt solution casting method to prepare protein film (Anker A., Foster GA., LoaderMA., Method of preparing gluten containing films and coatings. United States Patent (USP) 3.653,925,1972; Aydt TP., Weller CL., Testin RF., Mechanical and barrier properties of ediblecorn and wheat protein films.Trans.ASAE, 1991,34,207-211), improve protein solubility, and improve membrane material characteristic (Gennadios A. by heat or acid-alkali treatment, Brandenburg AH., WellerCL., Testin RF., Effect of pH on properties of wheat gluten and soy protein isolatefilms.J.Agric.Food.Chem., 1993,41:1835-1839; Roy S., Gennadios A., WellerCL., Zeece MG., Testin RF., Physical and molecular properties of wheat gluten filmscast from heated film-forming solutions.J.Food Sci., 1999,64:57-60).
Solution legal system film need consume a large amount of organic solvents, and is not suitable for the moulding of large size material or goods.People begin to explore the conventional forming technique of polymer and prepare protein material in recent years, disclose " preparation method of water-proof and heat-resistant plastic soybean protein film " as Chinese patent 00116036.2.Usually, strong interactions such as intermolecular hydrogen bonding, disulfide linkage make the thermoforming processing of protein material be difficult for implementing, and high temperature process easily causes the protein thermolysis.Thereby, need add a large amount of softening agent during the protein material thermoforming, to reduce molecular interaction, improve the molecular chain snappiness.Spendable softening agent has water or polyvalent alcohol such as glycerine, monose, disaccharides or oligose etc.Discoveries such as Mangavel, the mechanical property of the gluten powder film of thermoforming is better than solution casting film (Mangavel C., Rossignol N., Perronnet A., Barbot J., Popineau Y., Gueguen J., Properties and microstructure of thermo-pressed wheat gluten films:a comparisonwith cast films.Biomacromolecules, 2004,5,1596-1601).
In preparation plasticising protein composition process, strong shearing can make the intermolecular disulfide bond fracture, reduces protein molecular weight.Under comparatively high temps, form chemically crosslinked between the protein molecule again.This provides theoretical foundation for adopting conventional Process Technology of Polymer equipment to prepare the cross-linked type protein in grain plastics.Employing mechanically mixing such as Domenek prepare the plasticising gluten powder, adopt mould pressing method to prepare crosslinked sample (Domenek S., MorelMH., Redl A., Guilbert S., Rheological investigation of swollen gluten polymernetworks:effects of process parameters on cross-link density. Macrom.Symp., 2003,200:137-146), and investigate the plasticising gluten powder extrude complete processing (Pommet M., Redl A., MorelMH., Domenek S., Guilbert S., Thermoplastic processing ofprotein-based bioplastics:chemical engineering aspects of mixing, extrusion and hot molding.Macrom.Symp., 2003,197:207-218).
The mechanical property of grain protein material 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.Some can with the material of amino in the protein molecule, amide group, hydroxyl, thiol group generation chemical reaction, as halogenation acetic ester, diimine ester, two-n-hydroxyl-succinimide, dialdehyde or two ketone reagent, all can be used as proteinic chemical cross-linking agent, wherein the most frequently used is aldehydes reagent such as formaldehyde, oxalic dialdehyde or glutaraldehyde.
Protein plastic remains at present at two main drawbacks.One, even after crosslinked, the still remaining a large amount of hydrophilic radicals of protein molecule, material are easily suction in high humidity environment, and easily dehydration in low-humidity environment.Thereby the performance of protein plastic is affected by environment huge.They are two years old, though adopting the water-soluble polyol class is that softening agent improves proteinic processing characteristics and improves toughness of material, when protein plastic contacts with water or food containing water, the stripping gradually of polyalcohols softening agent, the fragility of protein plastic increases, even the forfeiture functions of use.
The present invention adopts double bond containing N-acylating agent that grain protein is carried out acylation modification, introduces double bond containing side chain on protein molecule, gives protein crosslinkable characteristic.It is new plasticizer that the present invention adopts nontoxic citrate or glyceryl ester, both given protein plasticity-processing characteristics, has solved softening agent again and has met the water-soluble shortcoming that goes out.Citrate that is adopted or glyceryl ester play significant plastification to protein, can significantly reduce proteinic second-order transition temperature.Simultaneously, the present invention adopts nontoxic lubricant, oxidation inhibitor and sanitas, further improves plasticity-processing, water tolerance and the performance such as ageing-resistant of cereal protein plastics, prolongs cereal protein plastics work-ing life.The essentially consist of protein molecule is that amido linkage can decompose in physical environment by the interconnective amino acid of amido linkage, thereby the prepared cross-linking type N-acylated grain protein plastics of the present invention can be degraded after discarded fully.Because the additive that is adopted is all nontoxic, the fodder additives that the N-acylated grain protein plastics after discarding can be used as fowl, poultry is used, for fowl, poultry provide rich in amino acid.
Summary of the invention
The purpose of this invention is to provide a kind of cross-linking type N-acylated grain protein degradable plastics and preparation method thereof.
Cross-linking type N-acylated grain protein degradable plastics comprises N-acylated grain protein 100 weight parts, softening agent 20～100 weight parts, lubricant 0.5～1.5 weight part, oxidation inhibitor 0.5～1.5 weight part, sanitas 0.1～1 weight part and linking agent 1～7 weight part.
The preparation method of N-acylated grain protein is; grain protein is pulverized; cross 100 order plugs, place N, be made into 5～15% suspension in the dinethylformamide; add the N-acylating agent that is equivalent to grain protein quality 10～20% in batches; under agitation condition, at 30～90 ℃ of reaction 2～8h, suction filtration; with solid product seasoning at room temperature, obtain the N-acylated grain protein.
The preparation method of cross-linking type N-acylated grain protein degradable plastics is; with N-acylated grain protein 100 weight parts; softening agent 20～100 weight parts; lubricant 0.5～1.5 weight part; oxidation inhibitor 0.5～1.5 weight part and sanitas 0.1～1 weight part carry out pre-mixing; then at 10～40 ℃ of mechanically milling 5～15min; in mixing process, add linking agent 1～7 weight part; obtain N-acylated grain protein composition; place mould; 1～3min colds pressing under room temperature and 5～20MPa pressure; temperature is risen to 110～160 ℃; hot pressing 10～30min obtains cross-linking type N-acylated grain protein degradable plastic product.
Grain protein is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin; The N-acylating agent is acrylate chloride, methacrylic chloride, 2-butylene acyl chlorides, 4-prenyl chloride, 10-undecene acyl chloride, cinnamyl chloride, oleoyl chloride, inferior oleoyl chloride, linolenic acid acyl chlorides, fumaryl chloride, acrylic anhydride, methacrylic anhydride, MALEIC ANHYDRIDE, 2-methyl-maleic acid acid anhydride or itaconic anhydride; Softening agent is triethyl citrate, tri-n-butyl citrate, citric acid tri-n-hexyl ester, trioctyl lemon acid, acetyl triethyl citrate, ATBC, the just own ester of acetyl tributyl citrate three, acetyl tributyl citrate three monooctyl esters, glyceryl monoacetate, glyceryl diacetate or triacetin; Lubricant is stearic acid, oxystearic acid, n-butyl stearate, single stearic acid glycerine lipoprotein, methyl hydroxystearate, soybean oil, peanut oil, Semen Maydis oil, Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or camellia seed oil; Oxidation inhibitor is 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-methylolphenol, tertiarybutylhydroquinone, butylhydroxy anisole, tea-polyphenol, tocopherol, Progallin A, Tenox PG, Stabilizer GA 8, lauryl gallate, gallic acid octadecyl ester, xitix, Quicifal or D-saccharosonic acid; Sanitas is sthyl sorbate, Sorbic Acid butyl p-hydroxybenzoate, dehydroacetic acid (DHA), Tegosept M, ethyl p-hydroxybenzoate or propylparaben; Linking agent is dicumyl peroxide, tert butyl isopropyl benzene peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-dual-tert-butyl peroxy hexane, the lauroyl peroxide tert-butyl ester or peroxidation phenylformic acid.
Advantage of the present invention is:
1) grain protein is a kind of renewable agricultural resource, and wide material sources are compared with petrochemical material and to be had inexhaustible advantage;
2) adopt double bond containing acyl chlorides or acid anhydrides that grain protein is carried out the N-acylation modification, on the grain protein molecule, introduce double bond containing side chain, can adopt superoxide to carry out crosslinked the grain protein molecule;
3) adopting citrate or glyceryl ester is new plasticizer, both given N-acylated grain protein plasticity-processing characteristics, has solved the shortcoming that material property relies on ambient moisture strongly again;
4) reagent of Cai Yonging all is safety, nontoxic, but the cross-linking type N-acylated grain protein degradable plastics contact food that is obtained, medicine etc. and do not cause pollution;
5) the cross-linking type N-acylated grain protein degradable plastics that is obtained can be used as fowl after discarding, animal fodder additive is used.
Embodiment
The grain protein that the present invention uses is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin.
Gluten powder also claims the active face strength flour, is to be the higher protein content material that raw material extracts through 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 high purity 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 03134973.0 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 or gluten powder 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.Botany Gazette, 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., 2005,53:306-312; Huang CP., Hejlsoe-Kohsel E., Han XZ., Protelytic activity in sorghum flour and its interferencein protein analysis.Cereal Chem., 2000,77:343-344 ".
The preparation of N-acylated grain protein is one of key of the present invention.The grain protein powder is placed non-proton medium N; in the dinethylformamide; be made into 5～15% suspension; add the N-acylating agent that is equivalent to grain protein quality 10～20% in batches; under agitation condition, at 30～90 ℃ of reaction 2～8h, suction filtration; with solid product seasoning at room temperature, obtain the N-acylated grain protein.N-acylating agent of the present invention is acyl chlorides or the acid anhydrides with two keys, and purpose mainly is to make amino or acyl group generation chemical reaction in N-acylating agent and the protein molecule, and two keys are introduced the protein molecular side chain, gives albumen crosslinkable characteristic.In addition, as the acyl chlorides of N-acylating agent or acid anhydrides also can with sulfydryl or the hydroxyl reaction on the protein molecule.
The N-acylation modification of grain protein carries out in water medium usually, with acid anhydrides such as diacetyl oxide or succinyl oxide is the N-acylating agent, needing additional concentrated alkali solution to keep pH in the reaction process is 8.0～8.5 (Zhang Hongyin, Zhu Jiajin, Zheng Xiao winter, seat Yu virtue, Wang Lan, wheat-gluten succinylation study on the modification. Scientia Agricultura Sinica, 2003,36 (3): 313-317; Zhang Hongyin, Fu Chengxin, Zheng Xiaodong, seat Yu virtue, Zhang Jian, wheat-gluten acetyl and succinylation modification to functional improve effect relatively reach the reaction mechanism pre-test. Chinese grain and oil journal, 2003,18 (4): 22-25).Because acid anhydrides is hydrolyzed to carboxylic acid in water, the active reduction, the N-acylation modification degree of grain protein is lower.The present invention adopts the bigger N of polarity first, and dinethylformamide is a non-protonization medium, has avoided the hydrolysis of N-acylating agent, makes the acidylate degree of grain protein improve greatly.
The preparation of N-acylated grain protein plasticity-processing compositions is one of key of the present invention.N-acylated grain protein, citrate or glyceryl ester softening agent, lubricant, oxidation inhibitor and sanitas are carried out pre-mixing; adopt conventional device of plastic processing to carry out mixing then to premixture; and the adding peroxide cross-linking agent, obtain N-acylated grain protein plasticity-processing compositions.The present invention is not very strict to premixed requirement, can adopt the mixing instrument of high-speed mixer or Haake, mixed at room temperature 2～10min under 50～3000r/min rotating speed; Also can the material elementary mixing evenly be got final product by the manual 10～30min that stirs of instrument.The pre-mixing material needs through mill or mixer mixing, adds linking agent and each component is mixed.
The N-acylated grain protein plasticity-processing compositions that is obtained at room temperature has excellent flowability, can realize flowing and mold filling under the effect of relative broad range pressure, and at high temperature can realize crosslinked.The crosslinking process that the present invention recommends is; N-acylated grain protein plasticity-processing compositions is placed mould, and the 1～3min that colds pressing under room temperature and 5～20MPa pressure rises to temperature 110～160 ℃ then; hot pressing 10～30min obtains cross-linking type N-acylated grain protein degradable plastic product.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
With the gluten powder is feedstock production cross-linking type N-acylated grain protein degradable plastics, may further comprise the steps:
1) takes by weighing the 100g gluten powder, pulverize, cross 100 order plugs, place N, in the dinethylformamide, mechanical stirring is made into 5% suspension, adds the acrylate chloride of 10g in batches, under agitation condition, at 30 ℃ of reaction 8h, suction filtration with solid product seasoning at room temperature, obtains N-acidylate gluten powder albumen;
2) take by weighing 100g N-acidylate gluten powder albumen; the 20g triethyl citrate; 0.5g stearic acid; 0.5g2; 6-di-tert-butyl-4-methy phenol and 0.1g sthyl sorbate; place in the high-speed mixer; mixed at room temperature 2min under the 3000r/min rotating speed; mixture is placed in the mill; at 10 ℃ of mixing 15min; and in mixing process, add the 1g dicumyl peroxide; obtain N-acidylate gluten powder protein composition; place GB/T1040-92 plastic tensile performance test Standard Module; adopt the vulcanizing press 3min that under room temperature and 5MPa pressure, colds pressing; temperature is risen to 110 ℃; hot pressing 30min, cooling; obtain the corn protein degradable plastic goods after the demoulding.
Embodiment 2:
With the rice protein powder is feedstock production cross-linking type N-acylated grain protein degradable plastics, may further comprise the steps:
1) takes by weighing the 100g rice protein powder, pulverize, cross 100 order plugs, place N, in the dinethylformamide, mechanical stirring is made into 15% suspension, adds the methacrylic chloride of 20g in batches, under agitation condition, at 90 ℃ of reaction 2h, suction filtration with solid product seasoning at room temperature, obtains N-acidylate rice protein;
2) take by weighing 100g N-acidylate rice protein; the 100g tri-n-butyl citrate; 1.5g oxystearic acid; 1.5g 2; 6-di-t-butyl-4-methylolphenol and 1g Sorbic Acid butyl p-hydroxybenzoate; place in the high-speed mixer; mixed at room temperature 10min under the 1000r/min rotating speed; mixture is placed in the mill; at 40 ℃ of mixing 5min; and in mixing process, add the 7g tert butyl isopropyl benzene peroxide; obtain N-acidylate rice protein composition; place GB/T1040-92 plastic tensile performance test Standard Module; adopt the vulcanizing press 1min that under room temperature and 20MPa pressure, colds pressing; temperature is risen to 160 ℃; hot pressing 10min, cooling; obtain the corn protein degradable plastic goods after the demoulding.
Embodiment 3:
With the wheat gliadin is feedstock production cross-linking type N-acylated grain protein degradable plastics, may further comprise the steps:
1) takes by weighing the 100g wheat gliadin, pulverize, cross 100 order plugs, place N, in the dinethylformamide, mechanical stirring is made into 10% suspension, adds the 2-butylene acyl chlorides of 15g, under agitation condition in batches, at 60 ℃ of reaction 5h, suction filtration with solid product seasoning at room temperature, obtains N-acidylate wheat gliadin;
2) take by weighing 100gN-acidylate wheat gliadin; the 60g citric acid tri-n-hexyl ester; the 1g n-butyl stearate; 1g tertiarybutylhydroquinone and 0.5g dehydroacetic acid (DHA); place in the mixing instrument of Haake; mixed at room temperature 5min under the 50r/min rotating speed; mixture is placed in the mill; at 30 ℃ of mixing 10min; and in mixing process, add the 4g ditertiary butyl peroxide; obtain N-acidylate wheat gliadin composition; place GB/T1040-92 plastic tensile performance test Standard Module; adopt the vulcanizing press 2min that under room temperature and 10MPa pressure, colds pressing; temperature is risen to 140 ℃, hot pressing 20min, cooling; obtain the corn protein degradable plastic goods after the demoulding.
Embodiment 4:
With the hordein is feedstock production cross-linking type N-acylated grain protein degradable plastics, may further comprise the steps:
1) takes by weighing the 100g hordein, pulverize, cross 100 order plugs, place N, in the dinethylformamide, mechanical stirring is made into 10% suspension, adds the 4-prenyl chloride of 15g, under agitation condition in batches, at 70 ℃ of reaction 4h, suction filtration with solid product seasoning at room temperature, obtains N-acidylate hordein;
2) take by weighing 100g N-acidylate hordein; the 60g trioctyl lemon acid; the 1g single stearic acid glycerine lipoprotein; 1g butylhydroxy anisole and 0.5g Tegosept M; place in the 200ml beaker; the manual 20min that stirs; mixture is placed in the mill; at 30 ℃ of mixing 10min; and in mixing process, add 4g 2; 5-dimethyl-2; 5-dual-tert-butyl peroxy hexane; obtain N-acidylate hordein composition; place GB/T1040-92 plastic tensile performance test Standard Module; adopt the vulcanizing press 2min that under room temperature and 10MPa pressure, colds pressing; temperature is risen to 140 ℃, hot pressing 20min, cooling; obtain the corn protein degradable plastic goods after the demoulding.
Embodiment 5:
With the zein is feedstock production cross-linking type N-acylated grain protein degradable plastics:
Replace gluten powder, replace acrylate chloride with the 10-undecene acyl chloride with zein, all the other conditions are with embodiment 1.
Embodiment 6:
With the kafirin is feedstock production cross-linking type N-acylated grain protein degradable plastics:
Replace rice protein powder, replace methacrylic chloride with cinnamyl chloride with kafirin, all the other conditions are with embodiment 2.
Embodiment 7～13:
Replace citric acid tri-n-hexyl ester with acetyl triethyl citrate, ATBC, the just own ester of acetyl tributyl citrate three, acetyl tributyl citrate three monooctyl esters, glyceryl monoacetate, glyceryl diacetate or triacetin respectively, all the other conditions are with embodiment 3.
Embodiment 14～22:
With methyl hydroxystearate, soybean oil, peanut oil, Semen Maydis oil, Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or the positive butyl ester of camellia seed oil place of magnesium stearate, all the other conditions are with embodiment 3 respectively.
Embodiment 23～32:
Replace tertiarybutylhydroquinone with tea-polyphenol, tocopherol, Progallin A, Tenox PG, Stabilizer GA 8, lauryl gallate, gallic acid octadecyl ester, xitix, Quicifal or D-saccharosonic acid respectively, all the other conditions are with embodiment 3.
Embodiment 33～34:
Replace the Sorbic Acid butyl p-hydroxybenzoate with ethyl p-hydroxybenzoate or propylparaben respectively, all the other conditions are with embodiment 3.
Embodiment 35～36:
Replace ditertiary butyl peroxide with the lauroyl peroxide tert-butyl ester or peroxidation phenylformic acid respectively, all the other conditions are with embodiment 3.
Embodiment 37～45:
Replace the 2-butylene acyl chlorides with oleoyl chloride, inferior oleoyl chloride, linolenic acid acyl chlorides, fumaryl chloride, acrylic anhydride, methacrylic anhydride, MALEIC ANHYDRIDE, 2-methyl-maleic acid acid anhydride or itaconic anhydride respectively, all the other conditions are with embodiment 3.
The invention provides a kind of cross-linking type N-acylated grain protein degradable plastics and preparation method thereof.Main raw material grain protein involved in the present invention belongs to renewable agricultural resource, wide material sources.The present invention adopts double bond containing acyl chlorides or acid anhydrides that grain protein is carried out the N-acylation modification; two keys are introduced the grain protein molecular side chain; the N-acylated grain protein is cooperated with non-toxic plasticizer, lubricant, oxidation inhibitor, sanitas, linking agent; crosslinked through thermoplasticity processing with hot press moulding, the grain protein degradable plastics of acquisition water tolerance and ageing-resistant performance excellence.
Claims (10)
1. cross-linking type N-acylated grain protein degradable plastics; it is characterized in that it comprises N-acylated grain protein 100 weight parts, softening agent 20～100 weight parts, lubricant 0.5～1.5 weight part, oxidation inhibitor 0.5～1.5 weight part, sanitas 0.1～1 weight part and linking agent 1～7 weight part.
2. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1; the preparation method who it is characterized in that described N-acylated grain protein is: grain protein is pulverized; cross 100 order plugs; place N; be made into 5～15% suspension in the dinethylformamide; add the N-acylating agent that is equivalent to grain protein quality 10～20% in batches; under agitation condition; at 30～90 ℃ of reaction 2～8h; suction filtration; with solid product seasoning at room temperature, obtain the N-acylated grain protein.
3. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 2 is characterized in that described grain protein is gluten powder, rice protein powder, wheat gliadin, hordein, zein or kafirin.
4. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 2; it is characterized in that described N-acylating agent is acrylate chloride, methacrylic chloride, 2-butylene acyl chlorides, 4-prenyl chloride, 10-undecene acyl chloride, cinnamyl chloride, oleoyl chloride, inferior oleoyl chloride, linolenic acid acyl chlorides, fumaryl chloride, acrylic anhydride, methacrylic anhydride, MALEIC ANHYDRIDE, 2-methyl-maleic acid acid anhydride or itaconic anhydride.
5. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1 is characterized in that described softening agent is triethyl citrate, tri-n-butyl citrate, citric acid tri-n-hexyl ester, trioctyl lemon acid, acetyl triethyl citrate, ATBC, the just own ester of acetyl tributyl citrate three, acetyl tributyl citrate three monooctyl esters, glyceryl monoacetate, glyceryl diacetate or triacetin.
6. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1; it is characterized in that described lubricant is stearic acid, oxystearic acid, n-butyl stearate, single stearic acid glycerine lipoprotein, methyl hydroxystearate, soybean oil, peanut oil, Semen Maydis oil, Rice pollard oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil or camellia seed oil.
7. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1; it is characterized in that; described oxidation inhibitor is 2; 6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-methylolphenol, tertiarybutylhydroquinone, butylhydroxy anisole, tea-polyphenol, tocopherol, Progallin A, Tenox PG, Stabilizer GA 8, lauryl gallate, gallic acid octadecyl ester, xitix, Quicifal or D-saccharosonic acid.
8. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1; it is characterized in that described sanitas is sthyl sorbate, Sorbic Acid butyl p-hydroxybenzoate, dehydroacetic acid (DHA), Tegosept M, ethyl p-hydroxybenzoate or propylparaben.
9. a kind of cross-linking type N-acylated grain protein degradable plastics according to claim 1; it is characterized in that; described linking agent is dicumyl peroxide, tert butyl isopropyl benzene peroxide, ditertiary butyl peroxide, 2; 5-dimethyl-2,5-dual-tert-butyl peroxy hexane, the lauroyl peroxide tert-butyl ester or peroxidation phenylformic acid.
10. the preparation method of a cross-linking type N-acylated grain protein degradable plastics as claimed in claim 1; it is characterized in that; with N-acylated grain protein 100 weight parts; softening agent 20～100 weight parts; lubricant 0.5～1.5 weight part; oxidation inhibitor 0.5～1.5 weight part and sanitas 0.1～1 weight part carry out pre-mixing; then at 10～40 ℃ of mechanically milling 5～15min; in mixing process, add linking agent 1～7 weight part; obtain N-acylated grain protein composition; place mould; 1～3min colds pressing under room temperature and 5～20MPa pressure; temperature is risen to 110～160 ℃; hot pressing 10～30min obtains cross-linking type N-acylated grain protein degradable plastic product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092511B (en) * | 2007-06-12 | 2010-05-26 | 浙江大学 | Easy-to-form degradable plastic of cross-linked type protein in grain, and preparation method |
| CN101851421B (en) * | 2009-03-31 | 2011-08-31 | 西南科技大学 | Thermoplastic plant protein/fiber blend material and preparation method thereof |
| CN103289417A (en) * | 2013-05-28 | 2013-09-11 | 河南工业大学 | Multi-modified soy protein biodegradable plastic and preparation method thereof |
| CN106819430A (en) * | 2016-12-28 | 2017-06-13 | 新昌县赛因斯生物科技有限公司 | Improve the feed formula of goat resistance against diseases |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52122287A (en) * | 1976-04-07 | 1977-10-14 | Sumitomo Bakelite Co Ltd | Anti-clouding composition |
| CN1055124C (en) * | 1996-12-12 | 2000-08-02 | 干信 | Process for preparing piptide acylate from protein of silk filature pupa by biological degradation |
| FR2766090B1 (en) * | 1997-07-15 | 1999-10-08 | Coletica | PARTICLES, IN PARTICULAR MICRO- OR NANOPARTICLES OF CROSS-LINKED VEGETAL PROTEINS, THEIR PREPARATION PROCESS AND COSMETIC, PHARMACEUTICAL OR FOOD COMPOSITIONS, CONTAINING |
| US6310105B1 (en) * | 2000-02-15 | 2001-10-30 | Wisconsin Alumni Research Foundation | Carboxyl-modified superabsorbent protein hydrogel |
| CN1159288C (en) * | 2001-09-17 | 2004-07-28 | 中国科学院过程工程研究所 | Protein modifier, preparation method and use thereof |
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2005
- 2005-08-26 CN CNB2005100604996A patent/CN100417693C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092511B (en) * | 2007-06-12 | 2010-05-26 | 浙江大学 | Easy-to-form degradable plastic of cross-linked type protein in grain, and preparation method |
| CN101851421B (en) * | 2009-03-31 | 2011-08-31 | 西南科技大学 | Thermoplastic plant protein/fiber blend material and preparation method thereof |
| CN103289417A (en) * | 2013-05-28 | 2013-09-11 | 河南工业大学 | Multi-modified soy protein biodegradable plastic and preparation method thereof |
| CN103289417B (en) * | 2013-05-28 | 2015-07-22 | 河南工业大学 | Multi-modified soy protein biodegradable plastic and preparation method thereof |
| CN106819430A (en) * | 2016-12-28 | 2017-06-13 | 新昌县赛因斯生物科技有限公司 | Improve the feed formula of goat resistance against diseases |
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| CN100417693C (en) | 2008-09-10 |
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