CN112322051A - Composite protein and preparation method and application thereof - Google Patents
Composite protein and preparation method and application thereof Download PDFInfo
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- CN112322051A CN112322051A CN202011333322.XA CN202011333322A CN112322051A CN 112322051 A CN112322051 A CN 112322051A CN 202011333322 A CN202011333322 A CN 202011333322A CN 112322051 A CN112322051 A CN 112322051A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides a composite protein and a preparation method and application thereof, wherein the composite protein is obtained by the reaction of zein, animal hair keratin and a chain extender, and the composite protein with higher molecular weight is obtained by the graft reaction of the zein, the animal hair keratin and the chain extender; when the composite protein is spun into fibers, the protein is not easy to run off, so that the prepared fiber product has high protein content, excellent drapability, antistatic property, moisture absorption, moisture permeability, air permeability and other properties; the preparation method of the compound protein is simple, convenient to operate and suitable for mass production and extraction.
Description
Technical Field
The invention belongs to the technical field of protein preparation, and particularly relates to a composite protein and a preparation method and application thereof.
Background
Wool, camel hair, human hair, pig bristle, bird feather and animal hair are mainly composed of keratin, the hair without textile value is dissolved to prepare solution, the solution can be processed into various fibers again by adopting an artificial spinning technology, the aim of recycling limited resources can be achieved, the raw material used for producing the corn protein is leftover material for preparing starch by processing corn, the raw material is easy to obtain, the raw material is spun by using common production equipment and processes, the extraction residue of the corn protein powder can be used as feed, the additional value of agricultural and animal byproducts is improved, and the social benefit and the economic benefit are very high.
At present, a lot of reports on protein extraction from corn raw materials in vegetable protein exist, and CN101024670 discloses an alkali-soluble corn protein and a preparation method and application thereof, wherein an aldehyde group is contained in a corn protein molecular chain segment, the molecular weight of the aldehyde group is 100-50000, raw materials are easy to obtain, the production process is simple, extracted residues can be used as feed, the prepared protein can be mixed and grafted with cotton pulp cellulose, wood pulp cellulose and bamboo pulp cellulose, filaments and short fibers with various specifications can be prepared by spinning through a wet spinning process, and a mulching film with high water vapor barrier property and oxygen barrier property can also be prepared. The raw materials used for producing the alkali-soluble zein are leftover materials of starch prepared by processing corns, so that the recycling of resources is realized, the additional value of agricultural and sideline products is improved, and the alkali-soluble zein has high social benefit and economic benefit. The disadvantage is that the protein is easy to lose in the using process of the protein extraction stock solution.
There are many methods for extracting keratin from animal hair, including oxidation, acidity, alkalinity, and reduction. CN1680467 discloses a method for extracting animal hair keratin stock solution from various wools, camels hair, pig bristles, human hair, fowl feather, animal hair and the like without textile value and application thereof, which comprises the steps of preparing a combined reducing agent by using sulfite, carbamide compounds and sodium salt organic matters, carrying out reduction treatment on raw material hair and preparing the animal hair keratin stock solution. The extracted keratin spinning solution can be mixed with a plurality of materials, such as nano-silver antibacterial materials, and then grafted and blended with cellulose according to a proper proportion to prepare spinning solution, and filaments or staple fibers are produced by wet equipment and processes. CN1680638 discloses a nano-silver inorganic antibacterial biological protein fiber, a preparation method and an application thereof, wherein the protein fiber contains 0.1-5.0 wt% of nano-silver inorganic antibacterial powder. The dry breaking strength of the fibers prepared by the method is as follows: 1.85-2.48 cN/dtex, elongation at break: 15.8-20.2%, and the wet breaking strength is 1.15-2.98cN/dtex, and the prepared product has excellent antibacterial property and wearability, and can be used for daily life such as clothes and the like or industrial application. However, there is also a tendency for the extracted protein to be lost during the spinning process, resulting in a lower final protein content.
Therefore, it is very important to develop a protein with simple process and convenient operation and a preparation method thereof, so as to obtain the composite protein with difficult loss of the protein in the spinning process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite protein and a preparation method and application thereof, wherein the composite protein is obtained by reacting zein, animal hair keratin and a chain extender, and has a molecular weight which is larger than that of the zein or the animal hair keratin, so that the protein is not easy to lose when the composite protein is spun with a cellulose stock solution; the preparation method of the compound protein is simple, convenient to operate and suitable for mass production and extraction.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a complex protein obtained by reacting zein, animal hair keratin and a chain extender.
Preferably, the molecular weight of the complex protein is 30000-120000 Da, such as 40000Da, 50000Da, 60000Da, 70000Da, 80000Da, 90000Da, 100000Da, 110000Da, and the specific points therebetween, which are not exhaustive and included in the range for brevity.
The composite protein provided by the invention is prepared by reacting the mixture of the corn protein and the animal hair keratin which are obtained by extraction with a chain extender; the reaction is grafting reaction, so that the composite protein with the molecular weight larger than that of the zein and the animal hair keratin is obtained, the composite protein is not easy to run off when being spun into fiber, the drapability, the antistatic property, the moisture absorption property, the moisture permeability, the air permeability and other properties of a fiber product are improved, and the application value is great.
Preferably, the chain extender comprises an aldehyde compound.
The chain extension of the invention comprises aldehyde compounds, wherein the aldehyde compounds can play a role in chain extension, and specifically, the aldehyde compounds can be condensed with amino groups in proteins to carry out covalent crosslinking so as to play a role in chain extension.
Preferably, the aldehyde compound includes any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing the complex protein according to the first aspect, the method comprising the steps of:
(1) mixing the zein supernatant and the animal wool keratin supernatant, and adding an acidic aqueous solution to obtain a corn/wool protein mixture;
(2) and (2) dissolving the corn/wool protein mixture obtained in the step (1) in an alkaline solution, and reacting with a chain extender to obtain the composite protein.
The preparation method of the composite protein provided by the invention comprises the steps of firstly mixing the extracted zein supernatant and the animal hair keratin supernatant, and separating out a corn/hair protein mixture under an acidic condition; and then, the separated corn/wool protein mixture and a chain extender are subjected to a grafting reaction under an alkaline condition to obtain the composite protein.
Preferably, the mass ratio of the zein supernatant to the animal hair keratin supernatant in the step (1) is 1 (0.1-10), such as 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1: 9.
Preferably, the mixing time in step (1) is 0.5-1 h, such as 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h or 0.95h, and the specific values therebetween are not exhaustive, and for brevity and clarity.
Preferably, the mixing in step (1) is carried out under stirring, more preferably under stirring at a rotation speed of 50-150 r/min (e.g. 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, 130r/min or 140 r/min).
Preferably, the acidic aqueous solution of step (1) comprises an aqueous solution of sulfuric acid.
Preferably, the solute content of the acidic aqueous solution in the step (1) is 5-15% by mass, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, after the acidic aqueous solution is added in step (1), the pH of the system is 4 to 6, for example, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6 or 5.8, and the specific values therebetween are not exhaustive, and for the sake of brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the mass ratio of the corn/wool protein mixture and the chain extender in the step (2) is 1 (0.005-0.03), such as 1:0.008, 1:0.01, 1:0.012, 1:0.014, 1:0.016, 1:0.018, 1:0.02, 1:0.022, 1:0.024, 1:0.026, 0.028, and the like.
Preferably, the chain extender comprises an aldehyde compound.
Preferably, the aldehyde compound includes any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two thereof.
Preferably, the alkaline solution of step (2) comprises a sodium hydroxide solution.
Preferably, the solute content of the alkaline solution in the step (2) is 3 to 15% by mass, for example, 3%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Preferably, the reaction temperature in the step (2) is 40-80 ℃, for example, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction in step (2) is carried out under stirring conditions, and more preferably under stirring conditions at a rotation speed of 50-150 r/min (e.g., 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, 130r/min, or 140 r/min).
Preferably, the reaction time in step (2) is 1.5-4.5 h, such as 1.7h, 1.9h, 2.1h, 2.3h, 2.7h, 3h, 3.2h, 3.4h, 3.6h, 3.9h, 4h or 4.2h, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the zein supernatant of step (1) is prepared by the following method:
(A1) mixing the raw material of the maize yellow powder and water, and filtering to obtain wet raw material of the maize yellow powder;
(A2) mixing the wet corn gluten meal raw material obtained in the step (A1), an alkaline aqueous solution and alcohol, and filtering to obtain the corn protein supernatant.
Preferably, the mass ratio of the water to the raw material of the maize yellow meal in the step (A1) is 1 (6-7), such as 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9 or 1: 7.
Preferably, the temperature of the mixing in the step (a1) is 30-40 ℃, for example, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃ or 39 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the mixing time in step (a1) is 0.25-1 h, such as 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h or 0.9h, and the specific values therebetween, which are not intended to be exhaustive for the sake of brevity and clarity.
Preferably, the wet corn gluten meal feedstock of step (a1) has a liquid loading of less than 50%, such as 40%, 35%, 30%, 25%, 20%, 15%, 10% or 5%, and the specific values therebetween are not exhaustive for the invention and are not intended to limit the scope to the specific values included in the ranges for brevity and conciseness.
Preferably, the mass ratio of the alkaline aqueous solution in the step (A2) to the wet maize yellow meal raw material in the step (A2) is 1 (0.5-1), such as 1:0.51, 1:0.0.52, 1:0.54, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8 or 1: 0.9.
Preferably, the mass ratio of the alcohol in the step (A2) to the basic aqueous solution in the step (A2) is 1 (1-4), such as 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, etc.
Preferably, the alcohol comprises ethanol and/or ethylene glycol.
Preferably, the basic aqueous solution of step (a2) comprises aqueous sodium hydroxide solution.
Preferably, the solute content of the alkaline aqueous solution in the step (a2) is 5 to 8% by mass, for example, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.5%, 6.8%, 7%, 7.2%, 7.5% or 7.8%, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive.
Preferably, the mixing in step (A2) is carried out under stirring conditions, more preferably under stirring conditions at a rotation speed of 150 to 400r/min (e.g., 160r/min, 170r/min, 200r/min, 240r/min, 280r/min, 320r/min, 340r/min, 360r/min, or 380 r/min).
Preferably, the temperature of the mixing in the step (a2) is 40 to 80 ℃, for example, 43 ℃, 46 ℃, 48 ℃, 52 ℃, 55 ℃, 58 ℃, 61 ℃, 64 ℃, 67 ℃, 70 ℃, 73 ℃, 76 ℃ or 79 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive listing of the specific values included in the range.
Preferably, the mixing time in step (a2) is 1.5-2.5 h, such as 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h or 2.4h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the animal hair keratin supernatant in the step (1) is prepared by the following method:
(B1) mixing animal hair with a dispersing agent, and filtering to obtain wet animal hair;
(B2) mixing the wet animal hair obtained in the step (B1) with an alkaline aqueous solution, and filtering to obtain the animal hair keratin hair supernatant.
Preferably, the mass ratio of the animal hair to the dispersant in the step (B1) is 1 (5-15), such as 1:5.4, 1:6, 1:7, 1:8, 1:9, 1:10, 1:10.6, 1:11, 1:12, 1:12.5, 1:13, 1:13.5 or 1: 14.
Preferably, the dispersant of step (B1) comprises a combination of a carbamide compound, a benzenesulfonate salt and a sulfite salt.
Preferably, the concentration of the amide-based compound in the dispersant is 0.8-3 mol/L, such as 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.4mol/L, 2.6mol/L or 2.8mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the concentration of the benzenesulfonate in the dispersant is 0.5 to 1.5mol/L, such as 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L or 1.4mol/L, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the concentration of the sulfite salt in the dispersant is 0.5-1.5 mol/L, such as 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L or 1.4mol/L, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the mixing in the step (B1) is 50 to 90 ℃, for example, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃, and the specific values therebetween are limited by the space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the mixing time in step (B1) is 0.5-2 h, such as 0.7h, 0.9h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h or 1.9h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the mass ratio of the wet animal hair in the step (B2) to the alkaline aqueous solution in the step (B2) is 1 (3-6), such as 1:3.3, 1:3.6, 1:3.9, 1:4.2, 1:4.5, 1:4.8, 1:5.1, 1:5.4 or 1: 5.7.
Preferably, the basic aqueous solution of step (B2) comprises an aqueous solution of sodium hydroxide.
Preferably, the solute content of the alkaline aqueous solution in the step (B2) is 5 to 12% by mass, for example, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11% or 11.5%, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention does not provide an exhaustive list of the specific values included in the range.
Preferably, the mixing in step (B2) is carried out under stirring conditions, more preferably under stirring conditions at a rotation speed of 150 to 400r/min (e.g., 160r/min, 170r/min, 200r/min, 240r/min, 280r/min, 320r/min, 340r/min, 360r/min, or 380 r/min).
Preferably, the temperature of the mixing in the step (B2) is 40 to 80 ℃, for example, 43 ℃, 46 ℃, 48 ℃, 52 ℃, 55 ℃, 58 ℃, 61 ℃, 64 ℃, 67 ℃, 70 ℃, 73 ℃, 76 ℃ or 79 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing time in step (B2) is 1.5-2.5 h, such as 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h or 2.4h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing the zein supernatant and the animal hair keratin supernatant in a mass ratio of 1 (0.1-10) for 0.5-1 h under the stirring condition of a rotating speed of 50-150 r/min, adding an acidic aqueous solution, and adjusting the pH value to 4-6 to obtain a corn/hair protein mixture;
the zein supernatant is prepared by the following steps:
(A1) mixing the raw material of the maize yellow powder and water, and filtering to obtain wet raw material of the maize yellow powder;
(A2) mixing the wet corn gluten meal raw material obtained in the step (A1), an alkaline aqueous solution and alcohol, and filtering to obtain a corn protein supernatant.
The animal hair keratin supernatant is prepared by the following steps:
(B1) mixing animal hair with a dispersing agent, and filtering to obtain wet animal hair; the dispersant comprises a combination of a carbamide compound, a benzene sulfonate and a sulfite;
(B2) mixing the wet animal hair obtained in the step (B1) with an alkaline aqueous solution, and filtering to obtain the keratin supernatant of the animal hair;
(2) mixing the corn/wool protein mixture obtained in the step (1), the alkaline aqueous solution and the chain extender for 1.5-4.5 hours under the stirring condition of 40-80 ℃ and the rotating speed of 50-150 r/min to obtain the composite protein; the mass percentage of the aldehyde compound in the chain extender is 0.5-3%; the aldehyde compound comprises any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two of the formaldehyde, the acetaldehyde and the glutaraldehyde.
In a third aspect, the present invention provides a composite protein stock solution comprising a composite protein as described in the first aspect.
Preferably, the falling ball viscosity of the composite protein stock solution is 20-80 s, such as 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s or 75s, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
The composite protein stock solution provided by the invention contains the composite protein, the viscosity of the composite protein stock solution is higher because the molecular weight of the composite protein is higher, and the falling ball viscosity outflow time of the composite protein stock solution is 20-80 s.
In a fourth aspect, the present invention provides a use of the composite protein stock solution according to the third aspect in the preparation of viscose fibers or tencel fibers.
Preferably, the viscose fiber is prepared by a method comprising mixing the composite protein stock solution and the alkaline aqueous solution with a viscose spinning stock solution, and spinning to obtain the viscose fiber.
Preferably, the tencel fiber is prepared by a method comprising mixing the composite protein stock solution according to the third aspect, an aqueous solution of N-methylmorpholine-N-oxide and a tencel spinning stock solution, and spinning to obtain the tencel fiber.
Compared with the prior art, the invention has the following beneficial effects:
the composite protein provided by the invention is obtained by reacting zein, animal hair keratin and a chain extender. The corn protein and animal hair keratin mixture obtained by extraction is subjected to grafting reaction by adopting a chain extender, so that the composite protein with higher molecular weight is prepared; when the composite protein is spun into fibers, the content of protein in the fibers is stable, and compared with the content of protein in the protein fibers prepared by adopting single protein in the prior art, the content of the protein in the composite protein fibers prepared by adopting the composite protein provided by the invention is increased by 50-180%, further, the composite protein provided by the invention is not easy to lose when being prepared into fibers;
secondly, the dry breaking strength of the composite protein viscose fiber obtained from the viscose protein fiber prepared from the composite protein stock solution prepared by the invention is 1.9-2.3 CN/dtex, the wet breaking strength is 1.2-1.4 CN/dtex, and the moisture regain is 13-15%, compared with the dry breaking strength (1.6-1.8 CN/dtex) of the viscose protein fiber prepared from the protein provided by the prior art, the dry breaking strength is improved by 6-44%, and the wet breaking strength (0.9-1.1 CN/dtex) is improved by 45-100%; the moisture regain (12%) is improved by 8-25%; the dry breaking strength of the composite protein tencel fiber prepared from the composite protein provided by the invention is 2.5-2.6 CN/dtex, the wet breaking strength is 1.7-2 CN/dtex, and the moisture regain is 16-17%, and is 39-63% higher than that (1.6-1.8 CN/dtex) of the dry breaking strength, 55-100% higher than that (1-1.1 CN/dtex) of the protein tencel fiber prepared from the protein in the prior art, and 23-31% higher than that (13%) of the wet breaking strength. Therefore, in conclusion, when the composite protein provided by the invention is prepared into a fiber product, the protein is not easy to run off, and the prepared fiber product has high protein content, excellent drapability, antistatic property, moisture absorption, moisture permeability, air permeability and other properties; the preparation method of the compound protein is simple, convenient to operate and suitable for mass production and extraction.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A zein supernatant is prepared by the following steps:
(1) mixing water and corn gluten (produced by Guangyu starch sugar Co., Ltd.) at a mass ratio of 1:6.5 at 35 deg.C for 0.5h, and press-filtering with plate-and-frame filter press to obtain wet corn material with liquid content of 40%;
(2) and (2) mixing 6% by mass of sodium hydroxide aqueous solution, the wet corn material obtained in the step (1) and ethanol at the mass ratio of 1:0.75:2.5 at the temperature of 60 ℃ and the stirring speed of 280r/min for 2h, and filtering to obtain the zein supernatant.
Preparation example 2
A wool keratin supernatant is prepared by the following steps:
(1) mixing a dispersant solution (a mixed solution of water as a solvent, 2mol/L carbamide, 1mol/L benzene sulfonate and 1mol/L sulfite) and wool at a mass ratio of 1:10 at 70 ℃ for 1.75h, and filtering by a centrifuge to obtain wet wool;
(2) and (2) mixing the wet wool obtained in the step (1) with the mass ratio of 1:4.5 and a 9% sodium hydroxide aqueous solution by mass percentage for 2 hours under the stirring condition of 60 ℃ and the rotating speed of 200r/min, and filtering to obtain the wool keratin supernatant.
Preparation example 3
A zein supernatant is prepared by the following steps:
(1) mixing water and corn gluten (produced by Guangyu starch sugar Co., Ltd.) at a mass ratio of 1:6 at 30 deg.C for 0.25h, and press-filtering with plate-and-frame filter press to obtain wet corn material with liquid content of 30%;
(2) and (2) mixing a 5% sodium hydroxide aqueous solution with a mass percentage of 1:0.5:1, the wet corn raw material obtained in the step (1) and ethylene glycol at 40 ℃ and a stirring speed of 150r/min for 1.5h, and filtering to obtain the zein supernatant.
Preparation example 4
A method for preparing a supernatant of a pig hair keratin comprises the following steps:
(1) mixing a dispersant solution (a solvent is water, and contains carbamide with the concentration of 0.8mol/L, benzene sulfonate with the concentration of 0.5mol/L and sulfite mixed solution with the concentration of 0.5 mol/L) and pig hair with the mass ratio of 1:5 at 50 ℃ for 0.5h, and filtering by adopting a centrifuge to obtain wet pig hair;
(2) and (3) mixing the wet pig hair obtained in the step (3) with a mass ratio of 1:3 and a 5% sodium hydroxide aqueous solution by mass percentage for 1.5h under the stirring condition of 40 ℃ and a rotation speed of 150r/min, and filtering to obtain the pig hair keratin supernatant.
Preparation example 5
A zein supernatant is prepared by the following steps:
(1) mixing water and corn gluten (produced by Guangyu starch sugar Co., Ltd.) at a mass ratio of 1:7 at 40 deg.C for 1h, and press-filtering with a plate-and-frame filter press to obtain a wet corn material with liquid content of 20%;
(2) and (2) mixing 8% of sodium hydroxide aqueous solution with the mass percentage of 1:1:4, the wet corn raw material obtained in the step (1) and ethanol at 80 ℃ and the stirring speed of 400r/min for 2.5h, and filtering to obtain the zein supernatant.
Preparation example 6
A method for preparing a supernatant of a pig hair keratin comprises the following steps:
(1) mixing a dispersant solution (a solvent is water, and contains 3mol/L carbamide, 1.5mol/L benzene sulfonate and 1.5mol/L sulfite mixed solution) and pig hair in a mass ratio of 1:15 at 90 ℃ for 2 hours, and filtering by adopting a centrifugal machine to obtain wet pig hair;
(2) and (3) mixing the wet pig hair obtained in the step (3) with the mass ratio of 1:6 and a sodium hydroxide aqueous solution with the mass percentage of 5% for 2.5 hours under the stirring condition of 80 ℃ and the rotating speed of 400r/min, and filtering to obtain the pig hair keratin supernatant.
Example 1
A complex protein having an average molecular weight of 85000 Da; the preparation method comprises the following steps:
(1) mixing the zein supernatant obtained in the preparation example 1 and the wool keratin supernatant obtained in the preparation example 2 in a mass ratio of 1:5 for 0.75h under the stirring condition of the rotating speed of 100r/min, adding a sulfuric acid aqueous solution with the mass percentage of 10% to adjust the pH value to 5, and obtaining a corn/wool protein mixture;
(2) and (2) dissolving the corn/wool protein mixture obtained in the step (1) in a sodium hydroxide solution with the mass percentage of 3% (the mass percentage of the corn/wool protein mixture in the sodium hydroxide solution is 40%), and then reacting the corn/wool protein mixture with a formaldehyde solution with the mass percentage of 0.5% for 3 hours under the stirring conditions of 60 ℃ and the rotating speed of 100r/min to obtain the composite protein.
Example 2
A complex protein having an average molecular weight of 30000 Da; the preparation method comprises the following steps:
(1) mixing the zein supernatant obtained in the preparation example 3 and the pig hair supernatant obtained in the preparation example 4 in a mass ratio of 1:0.1 for 0.5h under the stirring condition of a rotating speed of 50r/min, adding a sulfuric acid aqueous solution with a mass percentage of 5% to adjust the pH value to 6, and obtaining a corn/hair protein mixture;
(2) and (2) dissolving the corn/wool protein mixture obtained in the step (1) in a sodium hydroxide solution with the mass percentage of 3.5 percent, wherein the mass percentage of the corn/wool protein mixture in the sodium hydroxide solution is 30 percent, and then reacting the corn/wool protein mixture with a formaldehyde solution with the mass percentage of 0.8 percent for 1.5 hours under the stirring conditions of 40 ℃ and the rotating speed of 50r/min to obtain the composite protein.
Example 3
A complex protein having an average molecular weight of 120000 Da; the preparation method comprises the following steps:
(1) mixing the zein supernatant obtained in the preparation example 5 and the pig hair supernatant obtained in the preparation example 6 in a mass ratio of 1:10 for 1h under the stirring condition of the rotating speed of 150r/min, adding a sulfuric acid aqueous solution with the mass percentage of 15% to adjust the pH value to 4, and obtaining a corn/pig hair protein mixture;
(2) and (2) dissolving the corn/wool protein mixture obtained in the step (1) in a sodium hydroxide solution with the mass percentage of 6% (the mass percentage of the corn/wool protein mixture in the sodium hydroxide solution is 60%), and then reacting the corn/wool protein mixture with an acetaldehyde solution with the mass percentage of 1% for 4.5 hours under the stirring conditions of 80 ℃ and the rotating speed of 150r/min to obtain the composite protein.
Comparative example 1
A zein with an average molecular weight of 2000Da, its preparation method comprises the following steps:
adding a sulfuric acid aqueous solution with the mass percentage of 5% into the zein supernatant obtained in the preparation example 1 to adjust the pH to 5, thus obtaining the zein.
Comparative example 2
A wool keratin with an average molecular weight of 3000Da is prepared by the following steps:
adding a 5 mass percent sulfuric acid aqueous solution into the wool protein supernatant obtained in the preparation example 2 to adjust the pH to 5, thereby obtaining the wool keratin.
Comparative example 3
A pig hair keratin with average molecular weight of 3200Da is prepared by the following steps: adding a sulfuric acid aqueous solution with the mass percentage of 5% into the pig hair protein supernatant of the preparation example 4 to adjust the pH to 5, so as to obtain the pig hair keratin.
Application examples 1 to 3
A composite protein viscose fiber is prepared by respectively mixing the composite protein obtained in the embodiments 1-3 with a 5% sodium hydroxide aqueous solution to obtain a mixed solution (the mass percentage of the composite protein in the mixed solution is 20%), mixing the mixed solution with a viscose spinning solution (Baoding New fiber manufacturing Co., Ltd.) according to the mass ratio of 1:1, and performing wet spinning to obtain the composite protein viscose fiber.
Application examples 4 to 6
A composite protein tencel fiber is prepared by respectively mixing the composite protein obtained in the embodiments 1-3 with a 5% N-methylmorpholine-N-oxide aqueous solution (the mass percentage of the composite protein in the mixed solution is 20%), mixing the mixed solution with a tencel spinning stock solution (Baoding New type fiber manufacturing Co., Ltd.) according to the mass ratio of 1:1, and carrying out wet spinning.
Comparative application examples 1 to 3
A protein viscose fiber is prepared by respectively mixing the protein obtained in the comparative examples 1-3 with a 5% sodium hydroxide aqueous solution to obtain a mixed solution (the mass percentage of the composite protein in the mixed solution is 20%), mixing the mixed solution with a viscose spinning stock solution (a spinning stock solution of Baoding Swan New fiber manufacturing Co., Ltd.) according to the mass ratio of 1:1, and performing wet spinning to obtain the protein viscose fiber.
Comparative application examples 4 to 6
The egg day silk fiber is prepared by mixing the protein obtained in the comparative examples 1-3 with a 5% N-methylmorpholine-N-oxide aqueous solution to obtain a mixed solution (the mass percentage of the composite protein in the mixed solution is 20%), mixing the mixed solution with a day silk spinning solution according to the mass ratio of 1:1, and performing wet spinning.
And (3) performance testing:
(1) protein content: testing according to SN/T2115-2008 Dumas combustion method for detecting total nitrogen and crude protein in import and export foods and feeds;
(2) dry break strength, wet break strength and moisture regain: the test was carried out according to the standard of GBT 13758-.
The fibers prepared in application examples 1-6 and comparative application examples 1-6 were tested according to the test method, and the test results are shown in table 1:
TABLE 1
According to the data in the table 1, the composite protein fiber prepared by the composite protein provided by the invention has higher protein content and better moisture absorption performance; specifically, the protein content of the composite protein viscose fibers obtained in application examples 1 to 3 is 20 to 28%, which is 67 to 180% higher than the protein content (10 to 12%) of the protein viscose fibers provided in application examples 1 to 3, and the protein content of the composite protein tencel fibers obtained in application examples 4 to 6 is 30 to 35% higher than the protein content (14 to 20%) of the protein tencel fibers provided in application examples 50 to 150%, so that the protein content of the composite protein fibers prepared by using the composite protein provided by the invention is improved by 50 to 180% compared with the protein content of the protein fibers prepared by using a single protein in the prior art, and further, the composite protein provided by the invention is not easy to lose when being prepared into fibers.
Secondly, the dry breaking strength of the composite protein viscose fiber obtained in the application examples 1 to 3 is 1.9 to 2.3CN/dtex, the wet breaking strength is 1.2 to 1.4CN/dtex, and the moisture regain is 13 to 15 percent, which is improved by 6 to 44 percent compared with the dry breaking strength (1.6 to 1.8CN/dtex) and the wet breaking strength (0.9 to 1.1CN/dtex) of the viscose fiber obtained in the application examples 1 to 3, and is improved by 45 to 100 percent; the moisture regain (12%) is improved by 8-25%; the dry breaking strength of the composite protein tencel fiber obtained in the application examples 4-6 is 2.5-2.6 CN/dtex, the wet breaking strength is 1.7-2 CN/dtex, and the moisture regain is 16-17%, which is 39-63% higher than that (1.6-1.8 CN/dtex) of the composite protein tencel fiber obtained in the application examples 4-6, 55-100% higher than that (1-1.1 CN/dtex), and 23-31% higher than that (13%), thereby showing that the composite protein fiber prepared from the composite protein provided by the invention has good mechanical properties and moisture absorption properties.
The applicant states that the present invention is illustrated by the above examples to show a composite protein and the preparation method and application method thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The composite protein is characterized by being obtained by reacting zein, animal hair keratin and a chain extender.
2. The composite protein according to claim 1, wherein the molecular weight of the composite protein is 30000-120000 Da;
preferably, the chain extender includes an aldehyde compound;
preferably, the aldehyde compound includes any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two thereof.
3. A method for preparing the complex protein according to claim 1 or 2, comprising the steps of:
(1) mixing the zein supernatant and the animal wool keratin supernatant, and adding an acidic aqueous solution to obtain a corn/wool protein mixture;
(2) and (2) dissolving the corn/wool protein mixture obtained in the step (1) in an alkaline solution, and reacting with a chain extender to obtain the composite protein.
4. The preparation method according to claim 3, wherein the mass ratio of the zein supernatant fluid in the step (1) to the animal hair keratin supernatant fluid is 1 (0.1-10);
preferably, the mixing time in the step (1) is 0.5-1 h;
preferably, the mixing in the step (1) is carried out under the condition of stirring, and more preferably under the stirring condition with the rotating speed of 50-150 r/min;
preferably, the acidic aqueous solution of step (1) comprises an aqueous sulfuric acid solution;
preferably, the mass percentage of the solute in the acidic aqueous solution in the step (1) is 5-15%;
preferably, after the acidic aqueous solution is added in the step (1), the pH value of the system is 4-6.
5. The preparation method according to claim 3 or 4, wherein the mass ratio of the corn/wool protein mixture and the chain extender in the step (2) is 1 (0.005-0.03);
preferably, the chain extender includes an aldehyde compound;
preferably, the aldehyde compound comprises any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two thereof;
preferably, the alkaline solution of step (2) comprises a sodium hydroxide solution;
preferably, the mass percentage of the solute in the alkaline solution in the step (2) is 3-15%;
preferably, the reaction temperature in the step (2) is 40-80 ℃;
preferably, the reaction in the step (2) is carried out under the stirring condition, and more preferably under the stirring condition with the rotating speed of 50-150 r/min;
preferably, the reaction time in the step (2) is 1.5-4.5 h.
6. The method according to any one of claims 3 to 5, wherein the zein supernatant of step (1) is prepared by the following method:
(A1) mixing the raw material of the maize yellow powder and water, and filtering to obtain wet raw material of the maize yellow powder;
(A2) mixing the wet corn gluten meal raw material obtained in the step (A1), an alkaline aqueous solution and alcohol, and filtering to obtain the zein supernatant;
preferably, the mass ratio of the water to the raw materials of the maize yellow meal in the step (A1) is 1 (6-7);
preferably, the temperature of the mixing in the step (A1) is 30-40 ℃;
preferably, the mixing time of the step (A1) is 0.25-1 h;
preferably, the wet zeaxanthin feedstock of step (a1) has a liquid loading of less than 50%;
preferably, the mass ratio of the alkaline aqueous solution in the step (A2) to the wet maize yellow meal raw material in the step (A2) is 1 (0.5-1);
preferably, the mass ratio of the alkaline aqueous solution in the step (A2) to the alcohol in the step (A2) is 1 (1-4);
preferably, the alcohol comprises ethanol and/or ethylene glycol;
preferably, the basic aqueous solution of step (a2) comprises aqueous sodium hydroxide solution;
preferably, the mass percentage of the solute in the alkaline aqueous solution in the step (A2) is 5-8%;
preferably, the mixing in the step (A2) is carried out under stirring conditions, and more preferably under stirring conditions with the rotating speed of 150-400 r/min;
preferably, the temperature of the mixing in the step (A2) is 40-80 ℃;
preferably, the mixing time of the step (A2) is 1.5-2.5 h.
7. The method according to any one of claims 3 to 6, wherein the animal hair keratin supernatant of step (1) is prepared by:
(B1) mixing animal hair with a dispersing agent, and filtering to obtain wet animal hair;
(B2) mixing the wet animal hair obtained in the step (B1) with an alkaline aqueous solution, and filtering to obtain the keratin supernatant of the animal hair;
preferably, the mass ratio of the dispersing agent to the animal hair in the step (B1) is 1 (5-15);
preferably, the dispersant of step (B1) comprises a combination of a carbamide compound, a benzenesulfonate salt and a sulfite salt;
preferably, the concentration of the amide compound in the dispersant is 0.8-3 mol/L;
preferably, the concentration of the benzene sulfonate in the dispersant is 0.5-1.5 mol/L;
preferably, the concentration of the sulfite in the dispersant is 0.5-1.5 mol/L;
preferably, the temperature of the mixing in the step (B1) is 50-90 ℃;
preferably, the mixing time of the step (B1) is 0.5-2 h;
preferably, the mass ratio of the wet animal hair in the step (B2) to the alkaline aqueous solution in the step (B2) is 1 (3-6);
preferably, the basic aqueous solution of step (B2) comprises aqueous sodium hydroxide solution;
preferably, the mass percentage of the solute in the alkaline aqueous solution in the step (B2) is 5-12%;
preferably, the mixing in the step (B2) is carried out under stirring conditions, and more preferably under stirring conditions with the rotating speed of 150-400 r/min;
preferably, the temperature of the mixing in the step (B2) is 40-80 ℃;
preferably, the mixing time in the step (B2) is 1.5-2.5 h.
8. The production method according to any one of claims 3 to 7, characterized by comprising the steps of:
(1) mixing the zein supernatant and the animal hair keratin supernatant in a mass ratio of 1 (0.1-10) for 0.5-1 h under the stirring condition of a rotating speed of 50-150 r/min, adding an acidic aqueous solution, and adjusting the pH value to 4-6 to obtain a corn/hair protein mixture;
the zein supernatant is prepared by the following method:
(A1) mixing the raw material of the maize yellow powder and water, and filtering to obtain wet raw material of the maize yellow powder;
(A2) mixing the wet maize yellow powder raw material obtained in the step (A1), an alkaline aqueous solution and alcohol, and filtering to obtain a maize protein supernatant;
the animal hair keratin supernatant is prepared by the following method:
(B1) mixing animal hair with a dispersing agent, and filtering to obtain wet animal hair; the dispersant comprises a combination of a carbamide compound, a benzene sulfonate and a sulfite;
(B2) mixing the wet animal hair obtained in the step (B1) with an alkaline aqueous solution, and filtering to obtain the keratin supernatant of the animal hair;
(2) mixing the corn/wool protein mixture obtained in the step (1), the alkaline aqueous solution and the chain extender for 1.5-4.5 hours under the stirring condition of 40-80 ℃ and the rotating speed of 50-150 r/min to obtain the composite protein; the mass percentage of the aldehyde compound in the chain extender is 0.5-3%; the aldehyde compound comprises any one of formaldehyde, acetaldehyde or glutaraldehyde or a combination of at least two of the formaldehyde, the acetaldehyde and the glutaraldehyde.
9. A composite protein stock solution, comprising the composite protein of claim 1 or 2;
preferably, the falling ball viscosity outflow time of the composite protein stock solution is 20-80 s.
10. Use of a composite protein stock solution according to claim 9 in the preparation of viscose or tencel fibers;
preferably, the viscose is made by a process comprising: mixing the composite protein stock solution and the alkaline aqueous solution of claim 9 with a viscose spinning stock solution, and spinning to obtain the viscose;
preferably, the lyocell fibers are made by a process comprising: mixing the composite protein stock solution, the N-methylmorpholine-N-oxide aqueous solution and the tencel spinning stock solution according to the claim 9, and spinning to obtain the tencel fiber.
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| WO2020106366A2 (en) * | 2018-10-01 | 2020-05-28 | University Of Florida Research Foundation | Aldehyde crosslinking, protein based tissue scaffolds, and uses thereof |
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| GB963772A (en) * | 1961-06-05 | 1964-07-15 | Swift & Co | Method for improving the flocculating properties of proteinaceous materials |
| JP2004149953A (en) * | 2002-10-30 | 2004-05-27 | Kurabo Ind Ltd | Spinning dope for cellulose/protein compound fiber and cellulose/protein compound fiber |
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| US20150050857A1 (en) * | 2012-03-02 | 2015-02-19 | Johns Manville | Formaldehyde-free proteinaceous binder compositions |
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