CN113603920B - Method for secondary crosslinking of protein-based composite membrane material assisted by water vapor - Google Patents
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The invention relates to the technical field of crosslinking of high polymer materials, and discloses a method for secondary crosslinking of a water vapor auxiliary protein-based composite membrane material, which comprises the following steps: (1) preparation of a film forming liquid; (2) Adding a crosslinking agent into the film forming liquid, and stirring for 20-60 min at 40-60 ℃ to obtain a pre-crosslinked film forming liquid; (3) Preparing a pre-crosslinked protein-based composite membrane by a casting method or an electrostatic spinning method; (4) And placing the pre-crosslinked protein-based composite membrane in a water vapor atmosphere for secondary crosslinking treatment. The secondary crosslinking modified protein-based composite membrane obtained by the method has higher crosslinking degree, and can effectively improve the water resistance and mechanical property of the protein-based composite membrane under the condition of not affecting the film forming property.
Description
Technical Field
The invention relates to the technical field of crosslinking of high polymer materials, in particular to a method for secondary crosslinking of a water vapor auxiliary protein-based membrane material.
Background
For some membrane materials prepared from proteins (e.g., keratin, cottonseed protein, soy protein, etc.) or water-soluble polymers as the primary raw materials, they have poor water resistance or mechanical properties. Therefore, the membrane material needs to be crosslinked and modified, so that covalent bonds are built in molecules or among molecules of the membrane material to form a crosslinked network, thereby improving the water resistance and mechanical properties of the membrane material. The crosslinking method for the protein-based membrane material includes a physical crosslinking method, a microbial crosslinking method, and a chemical crosslinking method. Compared with physical crosslinking and microbial crosslinking, the chemical crosslinking method has more obvious crosslinking effect and more controllable crosslinking sites.
Common methods for chemical crosslinking of keratin materials are impregnation crosslinking, steam crosslinking and in situ crosslinking. Wherein, in-situ crosslinking is to directly add the crosslinking agent into the raw material solution to enable the raw material solution to undergo crosslinking reaction so as to achieve the effect of crosslinking modification. Compared with the impregnation crosslinking and the steam crosslinking, the in-situ crosslinking can effectively reduce the use amount of the chemical crosslinking agent, and the crosslinking agent molecules can fully and directly contact with the protein-based material, so that the crosslinking efficiency is effectively improved.
However, when the crosslinking agent is added to the raw material film-forming solution, the degree of gelation increases with the increase in the degree of crosslinking of the film-forming solution. This affects the fluidity of the solution, thereby reducing the film-forming property and spinnability of the solution, making it impossible to uniformly film or to spin successfully. At present, the method for solving the problems mainly comprises the step of controlling the crosslinking degree of a film forming solution after adding a crosslinking agent, namely casting film forming or electrostatic spinning film forming by using a film forming solution with lower crosslinking degree. Although this solution can smoothly form a film, it cannot effectively improve the water resistance and mechanical properties of the film material because of its low degree of crosslinking.
Therefore, a technology capable of assisting in secondary crosslinking of the protein-based membrane material is developed, the protein-based membrane material which is high in crosslinking degree and good in water resistance and mechanical property is prepared, the practicability of the protein-based composite membrane can be improved, and the application field can be further widened.
Disclosure of Invention
The invention provides a method for secondary crosslinking of a water vapor auxiliary protein-based membrane material, which comprises the following steps:
(1) Preparing a film forming liquid: adding the protein powder and the water-soluble polymer into a sample dissolving bottle, adding a cosolvent, and uniformly stirring to obtain a film forming liquid with the mass fraction of 6% -15%;
(2) Adding a crosslinking agent into the film forming liquid, and stirring for 20-60 min at 40-60 ℃ to obtain a pre-crosslinked film forming liquid;
(3) Preparing a pre-crosslinked protein-based composite membrane by a casting method or an electrostatic spinning method;
(4) And placing the pre-crosslinked protein-based composite membrane in a water vapor atmosphere for secondary crosslinking treatment.
The total solid mass of the protein powder and the water-soluble polymer is 1.20 g-3.0 g, and the mixing mass ratio is 9:1-5:5; the adding amount of the cross-linking agent is 3% -10% of the total solid mass of the protein powder and the water-soluble polymer.
Preferably, the protein powder in step (1) comprises one or more combinations of keratin or collagen or cottonseed protein or soy protein or zein.
Preferably, the cosolvent in the step (1) comprises an alkaline aqueous solution or a formic acid solution or hexafluoroisopropanol solution with a pH value of 8-11.
Preferably, the water-soluble polymer in step (1) comprises one or more combinations of polyvinyl alcohol or polyethylene oxide or polyethylene glycol or chitin or starch or carboxymethyl cellulose or gelatin.
Preferably, the cross-linking agent in step (2) comprises genipin or glutaraldehyde or glyoxal or formaldehyde or transglutaminase or dialdehyde starch or dialdehyde carboxymethyl cellulose.
Preferably, if the step (3) is to prepare the crosslinked modified protein-based composite film by adopting a casting method, placing a polypropylene or polyvinylidene fluoride or polyethylene mold filled with the pre-crosslinked film-forming liquid into a constant temperature and humidity box with the temperature of 25-35 ℃ and the relative humidity of 40-50%, and drying at constant temperature for 6-12 h.
Preferably, if the step (3) adopts an electrostatic spinning method to prepare the crosslinked modified protein-based composite membrane, placing the pre-crosslinked film-forming solution into a high-voltage electrostatic field for spinning, and continuously spinning for 6-10 hours to obtain the crosslinked modified protein-based composite nanofiber membrane. Wherein the electrostatic spinning process parameters are as follows: the voltage is 18-30 kV, the receiving distance is 8-15 cm, the spinning speed is 0.5-1.0 mL/h, the inner diameter of a spinning hole is 0.3-1.0 mm, the spinning temperature is 25-35 ℃, and the spinning humidity is 40-50%.
Preferably, the water vapor atmosphere in the step (4) is a constant temperature and constant humidity environment with a relative humidity of 75-90% and a temperature of 25-50 ℃, and the secondary crosslinking treatment time is 0.5-24 h.
Compared with the prior art, the invention has the following beneficial effects: 。
the invention utilizes the steam to assist the protein-based membrane material to carry out secondary crosslinking reaction, and can effectively improve the crosslinking degree of the protein-based membrane material, thereby improving the water resistance and mechanical property of the protein-based membrane material. In addition, the invention uses the water vapor as the medium for assisting the secondary crosslinking reaction of the protein-based membrane material, and has the characteristics of simple process, low cost, no toxicity or harm, strong applicability and the like.
Drawings
FIG. 1 is a graph showing the microscopic morphology of the samples of example 3, comparative example 1 and comparative example 2 before and after water absorption.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Preparing a film forming liquid: respectively adding 0.60g of keratin powder and 0.60g of polyvinyl alcohol into a sample dissolving bottle, adding a sodium hydroxide solution with the pH value of 9 as a cosolvent, and uniformly stirring to obtain a film forming solution with the mass fraction of 12%;
(2) Adding 0.072g of glutaraldehyde with the concentration of 50% into the film forming liquid, and stirring for 20min at 40 ℃ to obtain a pre-crosslinked film forming liquid;
(3) The pre-crosslinked keratin/polyvinyl alcohol composite nanofiber membrane is prepared through an electrostatic spinning method, the pre-crosslinked film-forming liquid is placed in a high-voltage electrostatic field for spinning, and the crosslinked modified protein-based composite nanofiber membrane is obtained after 8h of continuous spinning. Wherein the electrostatic spinning process parameters are as follows: the voltage is 18kV, the receiving distance is 15cm, the spinning speed is 0.5mL/h, the inner diameter of a spinning hole is 0.4. 0.4mm, the spinning temperature is 25 ℃, and the spinning humidity is 40%;
(4) And (3) placing the pre-crosslinked keratin/polyvinyl alcohol composite nanofiber membrane in a constant temperature and humidity environment with the relative humidity of 80% and the temperature of 40 ℃ for 6 hours, and performing secondary crosslinking treatment to obtain the secondarily crosslinked keratin/polyvinyl alcohol composite nanofiber membrane.
Example 2
(1) Preparing a film forming liquid: respectively adding 0.60g of keratin powder and 0.60g of polyvinyl alcohol into a sample dissolving bottle, adding a sodium hydroxide solution with the pH value of 9 as a cosolvent, and uniformly stirring to obtain a film forming solution with the mass fraction of 6%;
(2) Adding 0.072g of glutaraldehyde with the concentration of 50% into the film forming liquid, and stirring for 20min at 40 ℃ to obtain a pre-crosslinked film forming liquid;
(3) Preparing a crosslinked keratin/polyvinyl alcohol composite film by a casting method, placing a polypropylene mould filled with a pre-crosslinked film-forming liquid in a constant temperature and humidity box with the temperature of 25 ℃ and the relative humidity of 50%, and drying at constant temperature for 10 hours;
(4) And (3) placing the pre-crosslinked keratin/polyvinyl alcohol composite film in a constant temperature and humidity environment with the relative humidity of 80% and the temperature of 40 ℃ for 6 hours, and performing secondary crosslinking treatment to obtain the secondarily crosslinked keratin/polyvinyl alcohol composite film.
Example 3
(1) Preparing a film forming liquid: adding 0.36g of keratin powder and 0.84g of gelatin into a sample dissolving bottle, adding hexafluoroisopropanol solution as a cosolvent, and uniformly stirring to obtain a film forming solution with the mass fraction of 6%;
(2) Adding 0.06g of genipin into the film forming liquid, and stirring for 60min at 40 ℃ to obtain a pre-crosslinked film forming liquid;
(3) The pre-crosslinked keratin/gelatin composite nanofiber membrane is prepared by an electrostatic spinning method, the pre-crosslinked film-forming liquid is placed in a high-voltage electrostatic field for spinning, and the crosslinked modified protein-based composite nanofiber membrane is obtained after 8h continuous spinning. Wherein the electrostatic spinning process parameters are as follows: the voltage is 21kV, the receiving distance is 15cm, the spinning speed is 0.5mL/h, the inner diameter of a spinning hole is 0.4mm, the spinning temperature is 25 ℃, and the spinning humidity is 50%;
(4) And (3) placing the pre-crosslinked keratin/gelatin composite nanofiber membrane in a constant temperature and humidity environment with the relative humidity of 80% and the temperature of 35 ℃ for 24 hours, and performing secondary crosslinking treatment to obtain the secondarily crosslinked keratin/gelatin composite nanofiber membrane.
Comparative example 1
(1) Preparing a film forming liquid: adding 0.36g of keratin powder and 0.84g of gelatin into a sample dissolving bottle, adding hexafluoroisopropanol solution as a cosolvent, and uniformly stirring to obtain a film forming solution with the mass fraction of 6%;
(2) Adding 0.06g of genipin into the film forming liquid, and stirring for 60min at 40 ℃ to obtain a pre-crosslinked film forming liquid;
(3) The pre-crosslinked keratin/gelatin composite nanofiber membrane is prepared by an electrostatic spinning method, the pre-crosslinked film-forming liquid is placed in a high-voltage electrostatic field for spinning, and the crosslinked modified protein-based composite nanofiber membrane is obtained after 8h continuous spinning. Wherein the electrostatic spinning process parameters are as follows: the voltage is 21kV, the receiving distance is 15cm, the spinning speed is 0.5mL/h, the inner diameter of a spinning hole is 0.4mm, the spinning temperature is 25 ℃, and the spinning humidity is 50%.
Comparative example 2
(1) Preparing a film forming liquid: adding 0.36g of keratin powder and 0.84g of gelatin into a sample dissolving bottle, adding hexafluoroisopropanol solution as a cosolvent, and uniformly stirring to obtain a film forming solution with the mass fraction of 6%;
(2) The keratin/gelatin composite nanofiber membrane is prepared through electrostatic spinning, the pre-crosslinked film forming liquid is placed in a high-voltage electrostatic field for spinning, and the crosslinked modified protein-based composite nanofiber membrane is obtained after 8h of continuous spinning. Wherein the electrostatic spinning process parameters are as follows: the voltage is 21kV, the receiving distance is 15cm, the spinning speed is 0.5mL/h, the inner diameter of a spinning hole is 0.4mm, the spinning temperature is 25 ℃, and the spinning humidity is 50%;
(4) And (3) placing the pre-crosslinked keratin/gelatin composite nanofiber membrane in a constant temperature and humidity environment with the relative humidity of 80% and the temperature of 35 ℃ for 24 hours, and treating in a water vapor atmosphere to obtain the uncrosslinked keratin/gelatin composite nanofiber membrane.
The water vapor-assisted secondary cross-linked keratin/gelatin composite nanofiber membrane, the pre-cross-linked keratin/gelatin composite nanofiber membrane, and the uncrosslinked keratin/gelatin composite nanofiber membrane (prepared samples are respectively denoted as A, B, C) were prepared by using the same batch of extracted keratin and the same type of gelatin as raw materials and the same type of genipin as a cross-linking agent, respectively, according to the methods described in example 3, comparative example 1 and comparative example 2, and the microscopic morphologies before and after water absorption thereof were observed to evaluate the water resistance thereof, and the mechanical properties thereof were measured.
Microcosmic morphology testing: and cutting a small sample, sticking the small sample on a sample table stuck with conductive adhesive, performing metal spraying treatment on the sample, and observing the microscopic morphology of the sample under a scanning electron microscope with an accelerating voltage of 10 kV.
Mechanical property test: samples were cut to 75mm by 10mm dimensions, with a fixture spacing of 40mm, a draw rate of 5mm/min, and each sample was averaged 3 times.
The A sample is the keratin/gelatin composite nanofiber which is prepared according to the example 3, is added with the genipin crosslinking agent and is subjected to steam-assisted secondary crosslinking; the sample B is a keratin/gelatin composite nanofiber prepared according to comparative example 1, to which genipin cross-linking agent was added, but which was not subjected to steam-assisted secondary cross-linking; sample C is a keratin/gelatin composite nanofiber prepared according to comparative example 2 without the addition of a cross-linking agent but with steam treatment.
Table 1 shows the results of the mechanical properties of the respective samples.
| Sample of | Elongation at break (%) | Tensile strength (MPa) |
| A | 8.61 | 7.28 |
| B | 1.07 | 0.57 |
| C | 2.00 | 5.56 |
In contrast to the A, B, C sample, in terms of the microscopic morphology before and after water absorption, the a sample still maintains a good fibrous morphology after water absorption, the fibers swell but do not dissolve completely, while the B and C samples dissolve after water absorption, and the fibrous morphology has been lost. In terms of mechanical properties, the elongation at break and the tensile strength of the A sample are higher than those of the B sample and the C sample.
In the atmosphere of water vapor, hydrophilic groups such as free amino groups, hydroxyl groups and the like in keratin/gelatin molecular chains of the sample A can react with genipin molecules again, so that the number of the hydrophilic groups in the molecular chains is reduced, and the water resistance of the sample is effectively improved; a crosslinked network is formed, improving the mechanical properties of the sample. And because of the lack of the cross-linking agent or no water vapor treatment, more hydrophilic groups still exist in the molecular chains of the sample C and the sample B, a cross-linked network is not formed, and the water resistance is poor. This demonstrates that the degree of crosslinking of the membrane material can be effectively increased by a method of secondary crosslinking of the membrane material with the assistance of water vapor, thereby improving the water resistance and mechanical properties.
The foregoing has described in detail the technical solutions provided by the embodiments of the present invention, and specific examples have been applied to illustrate the principles and implementations of the embodiments of the present invention, where the above description of the embodiments is only suitable for helping to understand the principles of the embodiments of the present invention; also, variations in the detailed description and the application range will occur to those skilled in the art in light of the present disclosure. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (6)
1. A method for secondary crosslinking of a water vapor assisted protein based composite membrane material, comprising the steps of:
(1) Preparing a film forming liquid: adding the protein powder and the water-soluble polymer into a sample dissolving bottle, adding a cosolvent, and uniformly stirring to obtain a film forming liquid with the mass fraction of 6% -15%;
(2) Adding a crosslinking agent into the film forming liquid, and stirring for 20-60 min at 40-60 ℃ to obtain a pre-crosslinked film forming liquid;
(3) Preparing a pre-crosslinked protein-based composite membrane by a casting method or an electrostatic spinning method;
(4) Placing the pre-crosslinked protein-based composite membrane in a steam atmosphere for secondary crosslinking treatment;
the total solid mass of the protein powder and the water-soluble polymer is 1.20 g-3.0 g, and the mixing mass ratio is 9:1-5:5; the adding amount of the cross-linking agent is 3% -10% of the total solid mass of the protein powder and the water-soluble polymer.
2. The method of claim 1, wherein the protein powder in step (1) comprises one or more of keratin, collagen, cottonseed, soy, zein, and combinations thereof; the co-solvent comprises an alkaline aqueous solution or a formic acid solution or hexafluoroisopropanol solution with the pH value of 8-11; the water-soluble polymer comprises one or more combinations of polyvinyl alcohol or polyethylene oxide or polyethylene glycol or chitin or starch or carboxymethyl cellulose or gelatin.
3. The method of claim 1, wherein the crosslinking agent in the step (2) comprises genipin, glutaraldehyde, glyoxal, formaldehyde, transglutaminase, dialdehyde starch, dialdehyde carboxymethyl cellulose.
4. The method for secondary crosslinking of a protein-based composite membrane material assisted by water vapor according to claim 1, wherein in the step (3), if a crosslinked modified protein-based composite membrane is prepared by a casting method, a polypropylene or polyvinylidene fluoride or polyethylene mold containing a pre-crosslinked film-forming solution is placed in a constant temperature and humidity box with a temperature of 25-35 ℃ and a relative humidity of 40-50%, and is dried at constant temperature for 6-12 h.
5. The method for secondary crosslinking of the water vapor assisted protein based composite membrane material according to claim 1, wherein the step (3) is characterized in that if an electrostatic spinning method is adopted to prepare a crosslinked modified protein based composite membrane, a pre-crosslinked membrane forming solution is placed in a high-voltage electrostatic field for spinning, and the crosslinked modified protein based composite nanofiber membrane is obtained after 6-10 h of continuous spinning; wherein the electrostatic spinning process parameters are as follows: the voltage is 18-30 kV, the receiving distance is 8-15 cm, the spinning speed is 0.5-1.0 mL/h, the inner diameter of a spinning hole is 0.3-1.0 mm, the spinning temperature is 25-35 ℃, and the spinning humidity is 40-50%.
6. The method for secondary crosslinking of the protein-based composite membrane material assisted by water vapor according to claim 1, wherein the water vapor atmosphere in the step (4) is a constant temperature and constant humidity environment with a relative humidity of 75-90% and a temperature of 25-50 ℃, and the secondary crosslinking treatment time is 0.5-24 h.
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