CN110591390A - Dialdehyde starch crosslinked fiber/cottonseed protein composite material and preparation method and application thereof - Google Patents
Dialdehyde starch crosslinked fiber/cottonseed protein composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a dialdehyde starch crosslinked fiber/cottonseed protein composite material, and a preparation method and application thereof. According to the preparation method, cottonseed protein is used as a raw material, after denaturation, crosslinking and plasticization are carried out on the cottonseed protein, the cotton seed protein and alkalized fiber are subjected to hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material, the cottonseed protein is used as a matrix, the alkalized fiber is used as a reinforcing phase of the material, scanning electron microscope and infrared spectrum characterization are carried out on the structure of the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material, and mechanical property and thermogravimetric tests are carried out.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a dialdehyde starch crosslinked fiber/cottonseed protein composite material, and a preparation method and application thereof.
Background
With the shortage of traditional resources such as petroleum resources faced today and the environmental problems caused by petroleum as raw material, it is increasingly desired to find alternatives to petroleum, such as the production of biodegradable plastics to reduce white pollution. In the process of searching for petroleum raw material substitutes, people find that if the industrial production route of synthesizing degradable materials by effectively utilizing natural renewable resources is adopted, the production route completely accords with sustainable and recyclable economy. Plant proteins, agricultural by-products, have received increasing attention as a non-petroleum, biodegradable and renewable resource. The bioplastic produced by using agricultural and sideline product protein as raw material is called "second generation bioplastic" product, and is one of the current research hotspots.
At present, the researches on protein-based plastics at home and abroad mainly focus on soybean (isolated) protein, wheat gluten protein and the like, but few reports are made on the researches on cottonseed protein degradable plastics and the researches on synthesizing degradable high polymer materials by using cottonseed protein as a matrix. Meanwhile, besides developing the whole protein plastic with protein as the only high molecular material, the problem of low mechanical strength of the protein itself needs to be overcome.
Disclosure of Invention
In view of the above, the invention provides a dialdehyde starch crosslinked fiber/cottonseed protein composite material, a preparation method and an application thereof.
The specific technical scheme of the invention is as follows:
a preparation method of dialdehyde starch crosslinked fiber/cottonseed protein composite material comprises the following steps:
a) performing denaturation treatment on cottonseed protein to obtain modified cottonseed protein, and performing crosslinking reaction on the modified cottonseed protein and dialdehyde starch to obtain crosslinked cottonseed protein;
b) and plasticizing the crosslinked cottonseed protein, and then placing the plasticized crosslinked cottonseed protein and the radially distributed alkalized fibers in a mold for hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
Preferably, the protein content of the cottonseed protein in the step a) is 50% -60%;
the fibers in the alkalized fibers in the step b) are selected from one or more of sisal fibers, ramie fibers and flax fibers.
Preferably, before the hot press forming in step b), the method further comprises:
and (3) carrying out dipping treatment on the alkalized fiber by adopting a cross-linked cottonseed protein solution.
Preferably, the denaturant used in the denaturation treatment in the step a) is one or more selected from urea, heavy metal salt, strong acid and organic solvent;
the temperature of the denaturation treatment is 25-45 ℃;
the time of the denaturation treatment is 3 to 6 hours.
Preferably, the plasticizing agent used in the plasticizing process of the step b) is one or more selected from glycerol, acetamide, stearic acid, polypropylene glycol and butanediol;
the plasticizing treatment temperature is 30-50 ℃;
the plasticizing treatment time is 4-8 h.
Preferably, the plasticization is carried out using a twin-roll machine, with a roll gap of less than 1 mm.
Preferably, the temperature of the hot press molding in the step b) is 100-130 ℃;
the pressure of the hot-press molding is 20-50 Mpa;
the hot-press forming time is 4-15 min.
Preferably, the mass ratio of the cottonseed protein to the dialdehyde starch is 50: (5-40);
the mass ratio of the cottonseed protein to the alkalized fiber is 4: (0.1-0.4).
The invention also provides the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by the preparation method of the technical scheme.
The invention also provides the application of the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by the preparation method in the technical scheme in the field of packaging materials or agricultural films.
In summary, the invention provides a preparation method of a dialdehyde starch crosslinked fiber/cottonseed protein composite material, which comprises the following steps: a) performing denaturation treatment on cottonseed protein to obtain modified cottonseed protein, and performing crosslinking reaction on the modified cottonseed protein and dialdehyde starch to obtain crosslinked cottonseed protein; b) and plasticizing the crosslinked cottonseed protein, and then placing the plasticized crosslinked cottonseed protein and the radially distributed alkalized fibers in a mold for hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material. According to the preparation method, the cotton seed protein is used as a raw material, after the cotton seed protein is subjected to denaturation, crosslinking and plasticization, the cotton seed protein and the alkalized fiber are subjected to hot press molding to obtain the dialdehyde starch crosslinked fiber/cotton seed protein composite material, the cotton seed protein is used as a matrix, the alkalized fiber is used as a reinforcing phase of the material, the Scanning Electron Microscope (SEM) and infrared spectroscopy (FTIR) characterization is carried out on the structure of the prepared dialdehyde starch crosslinked fiber/cotton seed protein composite material, and mechanical property and thermogravimetric tests are carried out. And the dialdehyde starch is adopted for crosslinking, has crosslinking capacity and high chemical activity, forms covalent bonds and hydrogen bonds with polar groups in protein molecules, improves the tensile strength and the thermal stability of the dialdehyde starch crosslinked fiber/cottonseed protein composite material, and ensures that the dialdehyde starch crosslinked fiber/cottonseed protein composite material is environment-friendly and green.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a partial SEM image of a dialdehyde starch crosslinked fiber/cottonseed protein composite material in example 1 of the invention (bar 30 μm);
fig. 2 is a partial SEM image (bar 10 μm) of a dialdehyde starch crosslinked fiber/cottonseed protein composite material in example 1 of the invention;
fig. 3 is a cross-sectional SEM image (bar 200 μm) of dialdehyde starch crosslinked fiber/cottonseed protein composite material in example 2 of the invention;
fig. 4 is a cross-sectional SEM image of dialdehyde starch crosslinked fiber/cottonseed protein composite material in example 2 of the invention (bar 30 μm);
FIG. 5 is a graph of mechanical property parameters of dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by adopting dialdehyde starch of different weight parts in example 3 of the invention;
FIG. 6 is an FTIR chart of dialdehyde starch crosslinked fiber/cottonseed protein composite (CP/30DAS), DCP and CP in example 4 of the invention;
FIG. 7 is a thermogravimetric analysis graph of dialdehyde starch crosslinked fiber/cottonseed protein composite material (CP/5DAS/30GC, CP/20DAS/30GC and CP/20DAS/10GC) and DCP in example 5 of the invention;
FIG. 8 is a DTG graph of dialdehyde starch crosslinked fiber/cottonseed protein composite material (CP/5DAS/30GC, CP/20DAS/30GC and CP/20DAS/10GC) and DCP in example 5 of the invention.
Detailed Description
The invention provides a dialdehyde starch crosslinked fiber/cottonseed protein composite material as well as a preparation method and application thereof.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of dialdehyde starch crosslinked fiber/cottonseed protein composite material comprises the following steps:
a) performing denaturation treatment on the cottonseed protein to obtain modified cottonseed protein, and performing crosslinking reaction on the modified cottonseed protein and dialdehyde starch to obtain crosslinked cottonseed protein;
b) plasticizing the crosslinked cottonseed protein, and then placing the plasticized crosslinked cottonseed protein and the radially distributed alkalized fibers in a mold for hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
Dialdehyde starch (DAS) is an oxidized modified starch containing active aldehyde groups, is considered to be a modified starch with great potential and development prospect, and can become an important chemical raw material by combining the characteristic of starch property and aldehyde group property. The aldehyde functional group in the dialdehyde starch has alkali solubility, easy cross-linking grafting, strong cohesive force, difficult mildewing and low toxicity, and the aldehyde group on the dialdehyde starch can react with the amino group of proteins to generate Schiff alkali substances to replace cross-linking agents such as glyoxal, glutaraldehyde and the like.
In the preparation method, the cottonseed protein is used as a raw material, the cottonseed protein is subjected to denaturation, crosslinking and plasticization, and then the cottonseed protein and the alkalized fiber are subjected to hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material, the cottonseed protein is used as a matrix, the alkalized fiber is used as a reinforcing phase of the material, the alkalized fiber has high toughness and corrosion resistance, the alkalized fiber is used as the reinforcing phase of the cottonseed protein matrix to improve the mechanical property of the dialdehyde starch crosslinked fiber/cottonseed protein composite material, the Scanning Electron Microscope (SEM) and infrared spectroscopy (FTIR) characterization is carried out on the structure of the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material, and the mechanical property and thermogravimetric test are carried out, the result shows that the fiber of the dialdehyde starch crosslinked fiber/cottonseed protein composite material has good bonding effect with the cottonseed protein matrix, and the dialdehyde starch crosslinked fiber/cottonseed protein composite material has high tensile strength and Young modulus, has good mechanical property and strength and good thermal stability.
In addition, according to the embodiment of the invention, dialdehyde starch is adopted for crosslinking, the dialdehyde starch has crosslinking capacity and high chemical activity, and forms covalent bonds and hydrogen bonds with polar groups in protein molecules, so that the tensile strength and the thermal stability of the dialdehyde starch crosslinked fiber/cottonseed protein composite material are improved, the dialdehyde starch crosslinked fiber/cottonseed protein composite material is environment-friendly and green, the preparation method is simple in preparation process, convenient and fast to operate, the raw material source is wide, the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material is non-toxic and biodegradable, the brittleness of the dialdehyde starch crosslinked fiber/cottonseed protein composite material is improved, the toxicity of the dialdehyde starch crosslinked fiber/cottonseed protein composite material is reduced, and the preparation method can be applied to food packaging materials, industrial green packaging materials, cotton seed protein composite materials, cotton seed protein, cotton, The fields of biological medicine packaging materials, agricultural films and the like.
In the embodiment of the invention, the protein content of the cottonseed protein in the step a) is 50-60%.
The denaturant adopted in the denaturation treatment in the step a) is one or more selected from urea, heavy metal salt, strong acid and organic solvent, wherein the strong acid can be HNO3The organic solvent can be acetone, preferably urea, the denaturation treatment is carried out in solvent water by stirring, the concentration of the urea solution is 1M, the mass ratio of the cottonseed protein to the urea solution is preferably 1: 2-1: 8, and more preferably 1: 4;
the temperature of the denaturation treatment is 25-45 ℃, and preferably 35 ℃;
the time of the denaturation treatment is 3 to 6 hours, preferably 4 hours;
after the denaturation treatment, the pH value of the denatured cottonseed protein solution is preferably adjusted to 11-12, and the pH value is preferably adjusted by using a 1M NaOH solution.
In the embodiment of the invention, the mass ratio of the cottonseed protein to the dialdehyde starch is 50: (5-40), more preferably 50: (5-20).
The crosslinking reaction is preferably carried out under stirring, and the temperature of the crosslinking reaction is 60-80 ℃, and is preferably 70 ℃;
the time of the crosslinking reaction is 20min to 60min, preferably 30 min.
In the embodiment of the present invention, the crosslinked cottonseed protein obtained in step a) is a crosslinked cottonseed protein solution, and after step a) and before step b), the crosslinked cottonseed protein solution is preferably dried at a drying temperature of 70 ℃ to 100 ℃, preferably at a drying temperature of 80 ℃, for a drying time of 7h to 14h, preferably 10h, preferably by vacuum drying.
In the embodiment of the present invention, the fibers in the alkalized fibers in step b) are selected from one or more of sisal fibers, ramie fibers and flax fibers;
the alkalized fiber is preferably obtained by alkalization treatment by using a sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is preferably 5-20%.
In the embodiment of the present invention, the plasticizer used in the plasticizing process of step b) is one or more selected from glycerol, acetamide, stearic acid, polypropylene glycol and butanediol, and is preferably glycerol, and the mass ratio of the cottonseed protein to the glycerol is preferably 5: (1-3);
the plasticizing temperature is 30-50 ℃;
the plasticizing time is 4-8 h.
In the embodiment of the invention, the plasticizing treatment introduces the plasticizer into the protein plastic system, so that the Tg value of the protein plastic system can be effectively controlled, the subsequent processing can be carried out under mild (low temperature and low energy) conditions to prepare the degradable plastic, and the protein can be prevented from being decomposed and degraded at high temperature.
The plasticizing treatment is preferably carried out by adopting a double-roller machine, the gap between roller shafts is less than 1mm, the temperatures of the front roller shaft and the rear roller shaft of the double-roller machine are preferably 45 ℃, the directions of the front roller shaft and the rear roller shaft of the double-roller machine are positive rotation, and the purpose of adopting the double-roller machine is to better uniformly disperse the cross-linked cottonseed protein and the plasticizer, preferably disperse the cross-linked cottonseed protein and the plasticizer on the double-roller machine for 3-10 times, and more.
In the embodiment of the present invention, before the step b) of hot press forming, it is preferable that the method further includes: and (3) soaking the alkalized fiber by using a cross-linked cottonseed protein solution, and then drying, preferably freeze-drying to obtain the alkalized fiber which is an alkalized fiber preform.
In the embodiment of the invention, the temperature of the hot press molding in the step b) is 100-130 ℃;
the pressure of hot-press molding is 20-50 Mpa;
the time for hot press molding is 4-15 min.
The mass ratio of the cottonseed protein to the alkalized fiber is 4: (0.1-0.4), the length of the alkalized fibers is preferably 10cm, and the average diameter of the alkalized fibers is preferably 0.5 mm.
The preparation method provided by the embodiment of the invention has the advantages of simple operation process, low cost and economy, simple used instruments and equipment, and suitability for industrial production, the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material is green and degradable, and the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material has high mechanical property, is nontoxic and pollution-free, and can be widely applied to the fields of food packaging materials, industrial green packaging materials, biomedical packaging materials and the like.
The invention also provides the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by the preparation method of the technical scheme.
The invention also provides the application of the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by the preparation method in the field of packaging materials or agricultural films.
For a further understanding of the invention, reference will now be made in detail to the following examples.
In the specific embodiment, the adopted cottonseed protein is commercially available cottonseed protein powder special for fermentation.
Example 1
In this embodiment, the preparation of the dialdehyde starch crosslinked fiber/cottonseed protein composite material comprises the following steps:
1) weighing 50 parts by weight of cottonseed protein powder in a big beaker, adding 300mL of 1M urea solution, wherein the mass ratio of the cottonseed protein powder to the urea solution is 1:6, stirring for 4 hours at normal temperature for denaturation treatment to obtain denatured cottonseed protein solution, and adjusting the pH value of the denatured cottonseed protein solution to 12 by using 1M NaOH solution;
2) placing the modified cottonseed protein solution into a constant-temperature water bath kettle at 70 ℃ and mechanically stirring for 20min, then adding 10 parts by weight of dialdehyde starch, and continuing mechanically stirring for 30min to perform a crosslinking reaction to obtain a crosslinked cottonseed protein solution;
3) carrying out dip coating treatment on 0.15g of regularly arranged alkalized sisal fibers with the length of 10cm and the average diameter of 0.5mm by adopting 6g of cross-linked cottonseed protein solution, and then carrying out freeze drying to obtain sisal alkalized fiber preforms;
4) drying the residual cross-linked cottonseed protein solution in a vacuum drying oven at 80 ℃ for 10 hours, adding 15 parts by weight of glycerol for plasticizing, wherein the plasticizing is carried out by adopting a double-roller machine, so that the cross-linked cottonseed protein and the plasticizer are well and uniformly dispersed, the temperatures of front and rear roller shafts of the double-roller machine are both 45 ℃, the directions are positive rotation, and the gap between the roller shafts is less than 1 mm;
5) and (3) placing the plasticized crosslinked cottonseed protein and sisal fiber preform in a mold, and putting the mold on a hot press with the temperature of 100 ℃ and the pressure of 40MPa for hot press molding for 15min to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
Referring to fig. 1 and 2, which are partial SEM images of the dialdehyde starch crosslinked fiber/cottonseed protein composite material of example 1 of the invention, fig. 1 and 2 show that the surface of the fiber is covered with a layer of cottonseed protein film, which indicates that the fiber and the cottonseed protein matrix have good adhesion effect, and the cottonseed protein and the fiber have interface bonding, which can improve the mechanical properties of the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
Example 2
In this example, the preparation of the dialdehyde starch crosslinked fiber/cottonseed protein composite material is carried out, the method and the steps are the same as those of example 1, but the mass ratio of the cottonseed protein powder and the urea solution in the step 1) is 1:8, the weight part of the dialdehyde starch in the step 2) is 20 parts, the weight part of the glycerol in the step 4) is 30 parts, and the hot-press molding temperature in the step 5) is 130 ℃, the pressure is 20Mpa and the time is 4 min.
Referring to fig. 3 and 4, which are SEM images of cross-section of dialdehyde starch crosslinked fiber/cottonseed protein composite material of example 2 of the invention, fig. 3 and 4 show that the fiber and cottonseed protein matrix have a good bond, but there are gaps, which may be caused by uneven distribution of the fiber, but the bond of the dialdehyde starch crosslinked fiber/cottonseed protein composite material is good and tight, which indicates that the fiber/cottonseed protein composite material crosslinked by dialdehyde starch is successfully prepared in this example.
Example 3
In this embodiment, four dialdehyde starch crosslinked fiber/cottonseed protein composite materials are prepared, the method and the steps are the same as those of the embodiment 1, but the mass ratio of the cottonseed protein powder to the urea solution in the step 1) is 1:4, the weight parts of the dialdehyde starch in the step 2) are 2.5 parts, 5 parts, 10 parts and 15 parts in sequence, the weight part of the glycerol in the step 4) is 10 parts, the temperature for hot press molding in the step 5) is 120 ℃, the pressure is 28Mpa, and the time is 8min, and the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite materials are marked as CP/5DAS, CP/10DAS, CP/20DAS and CP/30DAS in sequence.
The mechanical properties of the urea-denatured modified cottonseed protein powder (DCP) and the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by using different weight parts of dialdehyde starch in example 3 were tested, and the results are shown in table 1 and fig. 5, where table 1 and fig. 5 show that, compared with DCP without crosslinking treatment (only urea-denatured treatment), the dialdehyde starch crosslinked fiber/cottonseed protein composite material with different weight parts of dialdehyde starch crosslinking has higher tensile strength and young's modulus, and the crosslinked network can effectively prevent the dialdehyde starch crosslinked fiber/cottonseed protein composite material from being greatly denatured under external tensile stress, so that the dialdehyde starch crosslinked fiber/cottonseed protein composite material has relatively better tensile strength. And when the weight portion of the cottonseed protein powder is 50 and the weight portion of the dialdehyde starch is 10, the dialdehyde starch crosslinked fiber/cottonseed protein composite material shows the optimal tensile strength and Young modulus, and the mechanical property is optimal. However, the elongation at break of DCP is the longest, indicating that the crosslinking treatment in the preparation method of the invention can not improve the toughness of the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
Table 1 example 3 mechanical property test results of dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by using dialdehyde starch of different weight parts
Example 4
The preparation method and the steps of the dialdehyde starch crosslinked fiber/cottonseed protein composite material are the same as those of the embodiment 1, but the mass ratio of the cottonseed protein powder and the urea solution in the step 1) is 1:2, the pH value of the modified cottonseed protein solution is adjusted to 11 by adopting 1M NaOH solution, the weight part of the dialdehyde starch in the step 2) is 15 parts, the weight part of the glycerol in the step 4) is 20 parts, the temperature of the hot-press molding in the step 5) is 110 ℃, the pressure is 36Mpa, and the time is 10min, so that the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite material is marked as CP/30 DAS.
FIG. 6 is an FTIR chart of a dialdehyde starch crosslinked fiber/cottonseed protein composite material (CP/30DAS), DCP (modified urea-denatured cottonseed protein powder) and CP (cottonseed protein powder) in example 4 of the invention, wherein the DCP is the modified urea-denatured cottonseed protein powder and the CP is the cottonseed protein powder, and in FIG. 6, the cottonseed protein powder subjected to denaturation and inactivation treatment by urea solution has a characteristic absorption of amide I band of 1648cm-1Transfer to lower frequency 1618cm-1(ii) a Characteristic absorption of amide II band from 1541cm-1Reduced to 1467cm-1. And, after denaturation, was crosslinked at 1665cm-1And a new absorption peak appears, and the absorption peak is judged to be an absorption peak of imine (-CN ═ N-) stretching vibration, and a test result shows that the dialdehyde starch and the cottonseed protein directly have a good crosslinking effect, and the dialdehyde starch can be used as a non-toxic crosslinking agent to be applied to the cottonseed protein, so that the application range of the cottonseed protein is widened.
Example 5
The preparation method and the steps of the three dialdehyde starch crosslinked fiber/cottonseed protein composite materials are the same as those of the embodiment 1, but the mass ratio of the cottonseed protein powder and the urea solution in the step 1) is 1:4, the pH value of the modified cottonseed protein solution is adjusted to 11.5 by adopting 1M NaOH solution, the weight part of the dialdehyde starch in the step 2) is 2.5 parts or 10 parts, the weight part of the glycerol in the step 4) is 5 parts or 15 parts, the temperature of the hot-press molding in the step 5) is 120 ℃, the pressure is 50Mpa, and the time is 5min, and the prepared dialdehyde starch crosslinked fiber/cottonseed protein composite materials are sequentially marked as CP/5DAS/30GC, CP/20DAS/30GC and CP/20DAS/10 GC.
Please refer to fig. 7, which is a thermogravimetric analysis graph of the dialdehyde starch crosslinked fiber/cottonseed protein composite material (CP/5DAS/30GC, CP/20DAS/30GC and CP/20DAS/10GC) and DCP of example 5 of the invention, wherein the DCP is denatured cottonseed protein powder denatured by urea, fig. 7 shows that the thermogravimetric analysis curve of the dialdehyde starch crosslinked fiber/cottonseed protein composite material mainly includes heat loss in three different stages, the first stage is less than 100 ℃, and the process is mainly an evaporation process of moisture; the second stage is 160-260 ℃, the stage is mainly the thermal decomposition of glycerol or urea, and the increase of the glycerol content can be reflected particularly from the graph of FIG. 8, and the thermal decomposition is correspondingly larger in the stage; the third stage is the thermal degradation of the dialdehyde starch crosslinked fiber/cottonseed protein composite material at the temperature of more than 260 ℃, and the process is accompanied by degradation and volatile gas CO2、CO、NH3And unsaturated compounds containing a carbonyl group. The final residual mass of the dialdehyde starch crosslinked fiber/cottonseed protein composite material is about 30 percent. The result shows that the dialdehyde starch crosslinked fiber/cottonseed protein composite material subjected to crosslinking plasticizing treatment shows better thermal stability relative to DCP, and compared with other dialdehyde starch crosslinked fiber/cottonseed protein composite materials, CP/20DAS/10GC shows the best thermal stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of dialdehyde starch crosslinked fiber/cottonseed protein composite material is characterized by comprising the following steps:
a) performing denaturation treatment on cottonseed protein to obtain modified cottonseed protein, and performing crosslinking reaction on the modified cottonseed protein and dialdehyde starch to obtain crosslinked cottonseed protein;
b) and plasticizing the crosslinked cottonseed protein, and then placing the plasticized crosslinked cottonseed protein and the radially distributed alkalized fibers in a mold for hot press molding to obtain the dialdehyde starch crosslinked fiber/cottonseed protein composite material.
2. The method according to claim 1, wherein the protein content of the cottonseed protein in step a) is 50% to 60%;
the fibers in the alkalized fibers in the step b) are selected from one or more of sisal fibers, ramie fibers and flax fibers.
3. The method of claim 1, wherein before the hot press forming in step b), further comprising:
and (3) carrying out dipping treatment on the alkalized fiber by adopting a cross-linked cottonseed protein solution.
4. The preparation method according to claim 1, wherein the denaturant used in the denaturation treatment in the step a) is one or more selected from urea, heavy metal salts, strong acids and organic solvents;
the temperature of the denaturation treatment is 25-45 ℃;
the time of the denaturation treatment is 3 to 6 hours.
5. The method according to claim 1, wherein the plasticizing process of step b) uses a plasticizer selected from one or more of glycerin, acetamide, stearic acid, polypropylene glycol and butanediol;
the plasticizing treatment temperature is 30-50 ℃;
the plasticizing treatment time is 4-8 h.
6. The method of claim 5, wherein the plasticizing process is performed using a twin roll machine, and the roll gap is less than 1 mm.
7. The preparation method according to claim 1, wherein the temperature of the hot press molding in the step b) is 100 ℃ to 130 ℃;
the pressure of the hot-press molding is 20-50 Mpa;
the hot-press forming time is 4-15 min.
8. The preparation method according to claim 1, wherein the mass ratio of the cottonseed protein to the dialdehyde starch is 50: (5-40);
the mass ratio of the cottonseed protein to the alkalized fiber is 4: (0.1-0.4).
9. The dialdehyde starch crosslinking fiber/cottonseed protein composite material prepared by the preparation method of any one of claims 1 to 8.
10. The application of the dialdehyde starch crosslinked fiber/cottonseed protein composite material prepared by the preparation method of any one of claims 1 to 8 in the field of packaging materials or agricultural films.
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