CN101851338B - Thermoplastic vegetable protein and preparation method thereof - Google Patents
Thermoplastic vegetable protein and preparation method thereof Download PDFInfo
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- CN101851338B CN101851338B CN 200910058758 CN200910058758A CN101851338B CN 101851338 B CN101851338 B CN 101851338B CN 200910058758 CN200910058758 CN 200910058758 CN 200910058758 A CN200910058758 A CN 200910058758A CN 101851338 B CN101851338 B CN 101851338B
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Abstract
The invention discloses a thermoplastic vegetable protein and a preparation method thereof. The thermoplastic vegetable protein comprises the following components in parts by weight: 20-100 parts of purified vegetable protein, 600-3000 parts of urea buffer solution, 20-100 parts of mercaptoethanol, 0.2-10 parts of initiator and 50-300 parts of ingrafted monomer. The preparation method comprises the following steps: after raw materials are smashed, adding NaOH solution of which the amount is 10 times of that of the raw materials and the pH is 8.0; processing for one hour at the temperature of 50 DEG C, filtering, decentralizing, and removing impurities; adjusting pH of the filtrate to 4.5 by sulfuric acid and then performing coagulation sedimentation, separation, washing and neutralization on the protein to obtain purified vegetable protein; stirring the purified vegetable protein and urea buffer solution of which the weight is 30 times of that of the purified vegetable protein in the presence of nitrogen at the temperature of 60 DEG C for 30 minutes; adding mercaptoethanol of which the weight is equivalent to that of the purified vegetable protein to react for 1 hour; fully extending protein modules in solution; respectively adding initiator and ingrafted monomer; leading in N2 to react at the temperature of 60 DEG C for 2-4 hours, and stopping reacting; after the reaction ends, fully precipitating by acetone; decentralizing and separating the obtained solid; and drying in vacuum after being washed to be neutral with water to obtain the product.
Description
(1) technical field
The present invention relates to a kind of protein, particularly a kind of vegetable-protein and preparation method thereof.
(2) background technology
Along with the day by day exhausted and human growing interest of Nonrenewable resources, how to utilize the green chemical industry product of renewable resources production environment-friendly types such as biomass to cause the attention of countries in the world industry member to environmental problem.Vegetable-protein is not only important food, health care, additive raw material, and also has a wide range of applications in non-food product fields such as chemical industry, environmental protection, military affairs, medicine.Utilizing the recyclability resource is the important content of the green hi-tech of current environment, is a long-range developing direction of protection environment, has significance far-reaching and reality.Vegetable-protein is a reproducibility biopolymer resource huge on the earth.From Sustainable utilization of resources, protection environment and biocompatible and Biodegradable characteristics, people have entrusted to the care of very big expectation for the utilization of energy regenerated vegetable-protein.Thereby the plant protein resource utilization, development environment close friend's green product, the hot fields in having formed the green high-tech research of environment and having developed.Vegetable-protein is as renewable resources, its modification and utilization can be saved the bulk petroleum resource on the one hand, the environmental pollution that a large amount of non-degraded synthesized polymer material wastes cause can be alleviated on the other hand, the circulation of biomass can be in physical environment, realized after vegetable-protein and material modified the discarding thereof.Vegetable-protein is used as thermoplastic packing material, blend, copolymeric material through the thermoplastic modification.The thermoplastic vegetable protein processing characteristics is good, in extrusion molding, blowing, injection moulding and foaming process, have good thermoplastic processing characteristics and mechanical property, degrade fully and environmental friendliness after its goods use, can be widely used in process for processing fields such as chemical industry, farmland film, electromechanics, material of construction, packing and environmental protection.
(3) summary of the invention
1, to the purpose of this invention is to provide a kind of be raw material with the natural plant protein to goal of the invention, and the method for production environment close friend's thermoplastic vegetable protein is the service that large-scale develops and utilizes of renewable resources vegetable-protein.
2, technical scheme technical scheme of the present invention is:
A kind of thermoplastic vegetable protein, the weight part proportioning of its each component is: purifying vegetable-protein 20～100, urea buffered soln 600～3000, mercaptoethanol 20～100, initiator 0.2～10, grafted monomer 50～300.Its preparation method is: the urea buffered soln of 30 times of purifying vegetable-protein and purifying protein weight is added in the reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add the mercaptoethanol reaction 1h suitable then with purifying vegetable-protein weight, protein molecule is fully stretched in solution, add initiator and grafted monomer more respectively, feed N simultaneously
2Stopped reaction behind reaction 2～4h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
The purifying vegetable-protein is to choose one or more plant protein materials in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran, pulverize, the NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight, handle 1h down at 50 ℃, filter, centrifugal, remove insoluble impurities, filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the purifying vegetable-protein.
After urea buffered soln is 10: 3 by volume the mixed of hydrochloric acid soln of 0.2mol/L trihydroxy-aminomethane solution and 0.2mol/L, add urea, make its concentration reach 8mol/L, promptly obtain urea buffered soln.
Initiator is selected potassium permanganate for use, Potassium Persulphate, Sodium Persulfate, ammonium persulphate and other persulphate, the arbitrary combination of one or more in hydrogen peroxide, benzoyl peroxide, lauroyl peroxide and other superoxide.
Grafted monomer can be selected vinylbenzene, vinylformic acid, vinyl cyanide, acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate, vinyl-acetic ester for use and contain the acids of ethylene linkage or one or more the arbitrary combination in the ester class.
Choose one or more plant protein materials in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran, pulverize, the NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight, handle 1h down at 50 ℃, filter, centrifugal, remove insoluble impurities, filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the purifying vegetable-protein; The urea buffered soln of 30 times of purifying vegetable-protein and purifying protein weight is added in the reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add the mercaptoethanol reaction 1h suitable then with purifying vegetable-protein weight, protein molecule is fully stretched in solution, add initiator and grafted monomer more respectively, feed N2 stopped reaction behind reaction 2～4h under 60 ℃ simultaneously; Reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.Thermoplastic vegetable protein can be used as thermoplastic packing material, blend, copolymeric material, is widely used for process for processing fields such as chemical industry, farmland film, electromechanics, material of construction, packing and environmental protection.
3, the beneficial effect biomass spread all over all over the world, and its resource quantity is huge, and form is various, on the earth turnout in plant every year just be equivalent to human at present consume mineral can 20 times, or be equivalent to 160 times of world's existing population food energy.Wood Adhesives from Biomass is the important directions of international biomass industry development, and the exhaustion of petrochemical industry resource, pollution have promoted the development of biomass macromolecular materials.Because the biomass macromolecular material has environmental friendliness characteristics such as renewable, degradable, the research and development of biomass-based macromolecular material and industrialization have become the focus of attracting attention in the whole world.The present invention is raw material with the vegetable-protein, forms the unformed shape macromole by vegetable-protein graft copolymerization, makes it have good thermoplasticity.The thermoplastic vegetable protein processing characteristics is good, in extrusion molding, blowing, injection moulding and foaming process, have good thermoplastic processing characteristics and mechanical property, degrade fully and environmental friendliness after its goods use, can be widely used in process for processing fields such as chemical industry, farmland film, electromechanics, material of construction, packing and environmental protection.
(4) embodiment
Below in conjunction with embodiment the present invention is described in further details, wherein said raw material umber is parts by weight except that specified otherwise.
Vegetable-protein purifying: choose one or more plant protein materials in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran, pulverize, the NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight, handle 1h down at 50 ℃, filter, centrifugal, remove insoluble impurities, filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the purifying vegetable-protein.
Embodiment 1: get 20 parts of purifying vegetable-proteins by weight, 600 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 20 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 50 parts in 0.2 part of ammonium persulphate and vinylformic acid more respectively, feed N simultaneously
2Stopped reaction behind reaction 2h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 2: get 100 parts of purifying vegetable-proteins by weight, 3000 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 100 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 300 parts of 10 parts of lauroyl peroxides and methyl acrylates more respectively, feed N simultaneously
2Stopped reaction behind reaction 4h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 3: get 40 parts of purifying vegetable-proteins by weight, 1200 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 40 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 2 parts in potassium permanganate more respectively, 100 parts of 2 parts of hydrogen peroxide and grafted monomer feed N simultaneously
2Stopped reaction behind reaction 2.5h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 4: get 60 parts of purifying vegetable-proteins by weight, 1800 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 60 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 2 parts of benzoyl peroxides, 4 parts of lauroyl peroxides and 100 parts of methyl acrylates, 80 parts of methyl methacrylates more respectively, feed N simultaneously
2Stopped reaction behind reaction 3h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 5: get 80 parts of purifying vegetable-proteins by weight, 2400 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 80 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 240 parts of 3 parts of initiator potassium persulfate, 5 parts of ammonium persulphates and vinyl-acetic esters more respectively, feed N simultaneously
2Stopped reaction behind reaction 3h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 6: get 50 parts of purifying vegetable-proteins by weight, 1500 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 50 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 5 parts of benzoyl peroxides and 50 parts of acrylamides, 100 parts of butyl acrylates more respectively, feed N simultaneously
2Stopped reaction behind reaction 3h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Embodiment 7: get 70 parts of purifying vegetable-proteins by weight, 2100 parts in urea buffered soln is in reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add 70 parts of reactions of mercaptoethanol 1h then, protein molecule fully stretches in solution, add 210 parts of 70 parts of ammonium persulphates and vinylbenzene more respectively, feed N simultaneously
2Stopped reaction behind reaction 3.5h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying, also can pass through extruding pelletization or hot-forming again.
Claims (3)
1. a thermoplastic vegetable protein is characterized in that, the weight part proportioning of its each component is: purifying vegetable-protein 20～100, urea buffered soln 600～3000, mercaptoethanol 20～100, initiator 0.2～10, grafted monomer 50～300; Its preparation process is: the first step vegetable-protein purifying, choose that one or more vegetable-proteins are raw material in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran; Plant protein material after the impurity elimination is pulverized; The NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight is handled 1h down at 50 ℃; Filter, centrifugal, remove insoluble impurities; Filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the purifying vegetable-protein; The second step graft copolymerization adds the urea buffered soln of 30 times of purifying vegetable-protein and purifying vegetable-protein weight in the reactor, stirs 30min in 60 ℃ under the condition of logical nitrogen; Add the mercaptoethanol reaction 1h suitable then, protein molecule is fully stretched in solution with purifying vegetable-protein weight; Add initiator and grafted monomer more respectively, feed N simultaneously
2Stopped reaction behind reaction 2～4h under 60 ℃; The 3rd step thermoplastic protein is separated, and reaction finishes the back and fully precipitates with acetone; Centrifugation gained solid after being washed to neutrality again vacuum-drying obtain; After described urea buffered soln is 10: 3 by volume the mixed of hydrochloric acid soln of 0.2mol/L trihydroxy-aminomethane solution and 0.2mol/L, add urea, make its concentration reach 8mol/L and obtain; Described grafted monomer is one or more the arbitrary combination of selecting for use in vinylbenzene, vinylformic acid, vinyl cyanide, acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate, the vinyl-acetic ester.
2. thermoplastic vegetable protein according to claim 1, it is characterized in that, described initiator is to select potassium permanganate for use, Potassium Persulphate, Sodium Persulfate, ammonium persulphate and other persulphate, the arbitrary combination of one or more in hydrogen peroxide, benzoyl peroxide, lauroyl peroxide and other superoxide.
3. prepare the method for the described thermoplastic vegetable protein of claim 1, the steps include:
The first step vegetable-protein purifying chooses that one or more vegetable-proteins are raw material in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran; Plant protein material after the impurity elimination is pulverized; The NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight is handled 1h down at 50 ℃; Filter, centrifugal, remove insoluble impurities; Filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the purifying vegetable-protein;
The second step graft copolymerization adds the urea buffered soln of 30 times of purifying vegetable-protein and purifying vegetable-protein weight in the reactor, stirs 30min in 60 ℃ under the condition of logical nitrogen; Add the mercaptoethanol reaction 1h suitable then, protein molecule is fully stretched in solution with purifying vegetable-protein weight; Add initiator and grafted monomer more respectively, feed N simultaneously
2Stopped reaction behind reaction 2～4h under 60 ℃;
The 3rd step thermoplastic protein is separated, and reaction finishes the back and fully precipitates with acetone; Centrifugation gained solid after being washed to neutrality again vacuum-drying obtain thermoplastic vegetable protein, also can carry out extruding pelletization or hot-forming again.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102250292A (en) * | 2011-04-29 | 2011-11-23 | 西南科技大学 | Thermoplastic animal protein and preparation method thereof |
| CN104003800A (en) * | 2014-05-30 | 2014-08-27 | 新疆慧尔农业科技股份有限公司 | Environment-friendly vegetable protein based efficient water and fertilizer slow/controlled-release material |
| CN107936194A (en) * | 2017-11-20 | 2018-04-20 | 郑州源冉生物技术有限公司 | A kind of protein plastic of high intensity and its preparation method and application |
| CN108912581B (en) * | 2018-07-10 | 2021-01-05 | 武汉工程大学 | Thermoplastic soybean protein composite material and preparation method thereof |
| CN114381865A (en) * | 2022-01-21 | 2022-04-22 | 广东工业大学 | Vegetable protein composite nanofiber membrane as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0976790A1 (en) * | 1998-07-27 | 2000-02-02 | Cargill BV | Process for the manufacture of composite materials |
| CN101362824A (en) * | 2008-09-27 | 2009-02-11 | 天津科技大学 | Method for preparing thermoplastic soy protein plastics |
| CN101486806A (en) * | 2009-02-17 | 2009-07-22 | 四川大学 | Natural polymer / degradable polymer composite material and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0976790A1 (en) * | 1998-07-27 | 2000-02-02 | Cargill BV | Process for the manufacture of composite materials |
| CN101362824A (en) * | 2008-09-27 | 2009-02-11 | 天津科技大学 | Method for preparing thermoplastic soy protein plastics |
| CN101486806A (en) * | 2009-02-17 | 2009-07-22 | 四川大学 | Natural polymer / degradable polymer composite material and preparation thereof |
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