CN117024609A - Crosslinked esterified modified microcrystalline cellulose and preparation method thereof - Google Patents
Crosslinked esterified modified microcrystalline cellulose and preparation method thereof Download PDFInfo
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- 229920000168 Microcrystalline cellulose Polymers 0.000 title claims abstract description 129
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- 229940016286 microcrystalline cellulose Drugs 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a crosslinked esterified modified microcrystalline cellulose and a preparation method thereof, which improve the aggregation phenomenon of microcrystalline cellulose by a double modification method of crosslinking and esterifying, and the prepared crosslinked esterified modified microcrystalline cellulose has nanoscale size and high crystallinity, has good mechanical property and biocompatibility, and is particularly suitable for the fields of biological scaffolds, tissue repair, drug delivery, biosensors and the like. The collagen composite matrix prepared by using the crosslinked esterified modified microcrystalline cellulose has better mechanical property, water absorption property and space structure stability, and brings new choices for biomedical material research and application.
Description
Technical Field
The invention belongs to the technical field related to medical foods, and particularly relates to crosslinked esterified modified microcrystalline cellulose and a preparation method thereof.
Background
Collagen, one of the most important structural proteins of the human body, is widely present in connective tissues, has excellent biocompatibility and bioactivity, and thus is widely used in the fields of biomedical materials, cosmetics, foods, health products, and the like. At present, various collagen composite matrixes prepared by taking collagen as a main raw material, such as wound dressing, artificial skin and the like, are commercialized into the market. The collagen composite matrix has mechanical properties similar to those of natural skin, can keep the wound moist, and is beneficial to wound healing. However, the collagen composite matrix in the prior art still has the problems of low supporting property and the like caused by poor mechanical properties, is unfavorable for cell adsorption and proliferation, and limits the application range thereof.
Microcrystalline cellulose is a biodegradable natural organic polymer material, and the main component of the microcrystalline cellulose is a linear polysaccharide substance combined by beta-1, 4-glucosidic bonds, and the microcrystalline cellulose is generally obtained by acid hydrolysis of the natural cellulose to a limit polymerization degree, and the microcrystalline cellulose takes the form of very fine short rods or powdery porous particles. The microcrystalline cellulose has the characteristics of larger specific surface area, high Young's modulus, high strength and the like; as a biological material, microcrystalline cellulose also has the characteristics of light weight, degradability, biocompatibility, reproducibility and the like. Therefore, in the prior art, microcrystalline cellulose having high mechanical strength and biodegradability is added to a composite collagen matrix in order to improve the mechanical properties of the matrix. Patent document CN 102886063B discloses a nano microcrystalline cellulose reinforced collagen composite matrix, and swelling property test shows that the composite matrix has a swelling rate of 500% after 500min at a content of 7wt% nano microcrystalline cellulose; the mechanical property test shows that the mechanical strength of the composite matrix is improved by 30 percent compared with that of a pure collagen scaffold.
Although the nano microcrystalline cellulose is adopted to improve the performance of the composite collagen matrix, the microcrystalline cellulose has abundant hydroxyl groups on the surface, has good hydrophilicity, is easy to form hydrogen bonds to cause aggregation, cannot be uniformly and stably dispersed in water, is unfavorable for the preparation of the collagen composite matrix, and further affects the mechanical property and water absorption of the collagen composite matrix.
Disclosure of Invention
In order to solve the problems of poor dispersibility of microcrystalline cellulose in water and low mechanical properties of the prepared collagen composite matrix in the prior art, the invention provides the crosslinked esterified modified microcrystalline cellulose and the preparation method thereof, the aggregation phenomenon of the microcrystalline cellulose is improved by a double modification method of crosslinking and esterifying, and the prepared crosslinked esterified modified microcrystalline cellulose has nanoscale size and high crystallinity and provides a new solution for preparing the reinforced composite collagen matrix.
The invention provides a preparation method of crosslinked esterified modified microcrystalline cellulose, which comprises the following steps:
s1, micronizing microcrystalline cellulose suspension, and adding a cross-linking agent for cross-linking reaction to obtain cross-linked modified microcrystalline cellulose;
s2, performing esterification reaction on the crosslinked modified microcrystalline cellulose prepared in the step S1 and soybean oil to prepare the crosslinked esterified modified microcrystalline cellulose.
In order to improve the dispersibility of the microcrystalline cellulose, so as to be better suitable for the preparation of the collagen composite matrix and further improve the mechanical property and the water absorption property of the matrix, the microcrystalline cellulose is subjected to double modification of crosslinking and esterification. In the invention, dialdehyde compounds are adopted as cross-linking agents, generally comprising glutaraldehyde and glyoxal, the dialdehyde compounds have two symmetrical aldehyde groups (-CHO), and can react with hydroxyl (-OH) in microcrystalline cellulose to generate hemiacetal, and then the hemiacetal is cross-linked to generate stable acetal compounds. The progress of the crosslinking reaction causes crosslinking bridges to be formed between the molecules of the microcrystalline cellulose, and crosslinking points between the molecules of the microcrystalline cellulose are increased. On the basis of crosslinking modification, the invention carries out esterification reaction on uncrosslinked hydroxyl (-OH) on microcrystalline cellulose and fatty acid in soybean oil. As a common vegetable oil, the soybean oil is easy to obtain raw materials, has good biocompatibility and biodegradability, contains various fatty acids including saturated fatty acids, monounsaturated fatty acids and polyunsaturated fatty acids, and is particularly rich in polyunsaturated fatty acids such as linoleic acid, linolenic acid and the like. The introduction of soybean oil fatty acid groups further increases the molecular weight and fiber strength of the crosslinked modified microcrystalline cellulose. The microcrystalline cellulose prepared by crosslinking and esterification modification has nanoscale size, high crystallinity and larger specific surface area, can be uniformly and stably dispersed in a solution, and greatly improves mechanical strength. Meanwhile, the crosslinked esterified modified microcrystalline cellulose has good biocompatibility and low toxicity, and is suitable for preparing biomedical materials. Therefore, the crosslinked esterified modified microcrystalline cellulose has important significance for preparing the enhanced collagen composite matrix, can further improve the mechanical properties of the enhanced collagen composite matrix on the basis of high water absorption of the pure collagen matrix, and expands the application range of the matrix.
Specifically, in step S1, the concentration of microcrystalline cellulose in the microcrystalline cellulose suspension is 20-30wt%; the microcrystalline cellulose may be commercially available or self-made, and commercially available conventional microcrystalline cellulose, such as nano microcrystalline cellulose, or co-processed products thereof, and the like, may be suitable for use in the present invention. The microcrystalline cellulose can also be prepared by mixing wood pulp with dilute sulfuric acid, heating for acidolysis, cooling, adding ammonia water for neutralization, press-filtering the neutralization solution, washing, drying, and sieving. The preparation method of the microcrystalline cellulose further preferably comprises the steps of mixing wood pulp with dilute sulfuric acid with the concentration of 5-20wt% according to the weight ratio of 1 (10-20), heating to 70-120 ℃ for acidolysis for 0.5-2 h, cooling to 50-70 ℃, and then adding ammonia water with the concentration of 10-30wt% for neutralization until the pH value is 5-7; pumping the neutralization solution into a plate-and-frame filter press for filter pressing, and washing with reverse osmosis water until the electric conductivity of the washing solution is less than 200uS.cm -1 Pressing to dry to obtain a microcrystalline cellulose filter cake; the filter cake is sent into a flash dryer for drying, the parameters of the flash dryer are set as follows, the air inlet temperature is 130-160 ℃,the temperature of the air outlet is 60-90 ℃. And sieving the dried filter cake by adopting a 80-100 mesh rotary vibrating screen to obtain microcrystalline cellulose.
Preferably, in step S1, the crosslinking agent is selected from one or two of glutaraldehyde and glyoxal. In a typical dialdehyde crosslinking agent, the amount of methylene groups present between two pairs of carbonyl groups has a certain influence on the binding action of crosslinking points, and thus the crystallinity and fiber strength of microcrystalline cellulose are affected. In addition, the crosslinking modification of the microcrystalline cellulose can also control the crosslinking degree and the formation of a crosslinked structure by adjusting the concentration of the crosslinking agent, the reaction conditions and other parameters.
Preferably, in step S1, the amount of the crosslinking agent added is 0.1 to 2wt.% of microcrystalline cellulose, more preferably 0.3 to 1.5wt.%.
Preferably, in step S1, the micronization treatment includes ball milling, high-pressure homogenization, emulsification, and the like, and more preferably, the ball milling treatment.
Preferably, in step S1, the temperature of the crosslinking reaction is 40 to 60 ℃ and the time is 2 to 4 hours.
Preferably, in step S2, soybean oil is added in an amount of 20 to 50wt.% of microcrystalline cellulose by mass.
Preferably, in the step S2, the esterification reaction uses ethanol as a solvent, and the mass ratio of the soybean oil to the ethanol is 1 (0.8-1.2), and more preferably 1:1.
Preferably, in step S2, the temperature of the esterification reaction is 100 to 150 ℃ and the time is 3 to 4 hours.
Preferably, in the step S2, after the esterification reaction, the obtained reaction liquid is subjected to spray drying, iron removal and sieving to obtain the crosslinked esterified modified microcrystalline cellulose.
Preferably, the spray drying treatment is performed by a spray dryer; the spray dryer parameters were set as follows: the air inlet temperature is 170-200 ℃ and the air outlet temperature is 60-90 ℃.
Preferably, the iron removal treatment is completed through an iron remover, and the parameter of the iron remover is set to 10000-120000 gauss. In the preparation process of the medical auxiliary material, an iron remover is generally utilized to remove iron impurities in the material, so as to improve the quality of the product and avoid the reaction of active components in the medical material and the iron impurities.
Preferably, collecting the material after iron removal, and sieving the material with an ultrasonic sieve of 80-100 meshes to obtain the crosslinked esterified modified microcrystalline cellulose.
The invention also provides the crosslinked esterified modified microcrystalline cellulose which is prepared by the preparation method. The crosslinked esterified modified microcrystalline cellulose can be applied to the fields of biological scaffolds, three-dimensional printing construction, tissue repair, drug delivery, controlled release systems and the like. Specifically, the crosslinked esterified modified microcrystalline cellulose has good mechanical strength and stable space structure, can be used for preparing biological scaffolds, supports the attachment, proliferation and differentiation of cells, and promotes the regeneration and repair of tissues. The crosslinked esterified modified microcrystalline cellulose has larger specific surface area, is favorable for the absorption and the sustained release of the medicine, and can be used as a medicine carrier for preparing a controlled release medicine conveying system to realize the sustained release of the medicine. The crosslinked esterified modified microcrystalline cellulose can also be used as a base material of a biosensor, and the preparation of the biosensor with high sensitivity and high stability is realized by utilizing the characteristic of high crystallization and larger surface area of the crosslinked esterified modified microcrystalline cellulose.
The invention also provides a collagen composite matrix, which comprises the crosslinked esterified modified microcrystalline cellulose. Further, the collagen composite matrix comprises 0.05-1 wt% of microcrystalline cellulose. Compared with the prior art, the collagen composite matrix provided by the invention has a stable space structure, better swelling performance and mechanical performance, and can be applied to the fields of wound dressing, tissue-induced regeneration membrane, soft tissue patch, tissue engineering skin, facial mask and the like.
The invention has the beneficial effects that: the preparation method of the crosslinked esterified modified microcrystalline cellulose provided by the invention is simple, has nanoscale size and high crystallinity, is not easy to agglomerate in aqueous solution, has good mechanical properties and biocompatibility, and is particularly suitable for the fields of biological scaffolds, tissue repair, drug delivery, biological sensors and the like. Compared with the prior art, the collagen composite matrix prepared by using the crosslinked esterified modified microcrystalline cellulose has better mechanical property, water absorption property and space structure stability, and brings new choices for biomedical material research and application. Meanwhile, the modification method of crosslinking before esterification provided by the invention brings new thought for improving the performance of microcrystalline cellulose.
Detailed Description
The following specific examples are presented to illustrate the present invention, and those skilled in the art will readily appreciate the additional advantages and capabilities of the present invention as disclosed herein. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. The methods used in the examples of the present invention are conventional methods, and the reagents used are commercially available.
Example 1:
the embodiment provides a crosslinked esterified modified microcrystalline cellulose, and the preparation method thereof specifically comprises the following steps:
preparation of microcrystalline cellulose: 200kg of wood pulp and 10wt.% of dilute sulfuric acid are mixed in a reaction kettle according to the mass ratio of 1:15, acidolysis is carried out for 1.5 hours in the temperature range of 95-100 ℃ to obtain acidolysis solution, the acidolysis solution is cooled to 65 ℃, 15wt.% of ammonia water is added into the acidolysis solution to adjust the pH value to 6.5, the neutralization solution is pumped into a plate-and-frame filter press for filter pressing, and then primary reverse osmosis water is added for washing until the electric conductivity of the washing solution is less than 200uS.cm -1 And pressing to dry to obtain a microcrystalline cellulose filter cake. And (3) sending the filter cake into a flash dryer to be dried at the air inlet temperature of 150-160 ℃ and the air outlet temperature of 80-90 ℃, collecting the dried material, and sieving with a 100-mesh ultrasonic sieve to obtain the microcrystalline cellulose.
Crosslinking modification: the microcrystalline cellulose prepared above was prepared into a 20wt.% suspension with pure water, and subjected to micronization treatment with a ball mill at a rotation speed of 500r/min for 60 minutes. Transferring the feed liquid into a crosslinking reaction kettle, adding glutaraldehyde accounting for 0.3wt.% of the weight of the microcrystalline cellulose, and stirring and reacting for 3 hours at 55 ℃ to obtain the crosslinked modified microcrystalline cellulose.
Esterification modification: adding soybean oil and ethanol mixed solution into the reaction kettle with the crosslinked modified microcrystalline cellulose, wherein the soybean oil accounts for 20wt.% of the weight of the microcrystalline cellulose, and the ethanol accounts for 20wt.% of the weight of the microcrystalline cellulose, and uniformly stirring and reacting for 4 hours at a temperature ranging from 110 ℃ to 115 ℃ to obtain a reaction solution.
Spray drying: pumping the reaction liquid into a spray dryer to carry out spray drying under the conditions that the air inlet temperature is 190-200 ℃ and the air outlet temperature is 80-90 ℃. Collecting the sprayed and dried material, removing iron under the condition of 80000 gauss by an iron remover, sieving by a 100-mesh ultrasonic sieve after iron removal is finished, and sieving to obtain crosslinked esterified modified microcrystalline cellulose which is a sample I.
Example 2:
this example provides another crosslinked esterified modified microcrystalline cellulose, prepared in substantially the same manner as in example 1, except that glutaraldehyde was added in an amount of 0.05wt.% based on the weight of microcrystalline cellulose to produce sample two.
Example 3:
this example provides another crosslinked esterified modified microcrystalline cellulose, prepared in substantially the same manner as in example 1, except that glutaraldehyde was added in an amount of 1wt.% based on the weight of microcrystalline cellulose to produce sample three.
Example 4:
this example provides another crosslinked esterified modified microcrystalline cellulose, prepared in substantially the same manner as in example 1, except that glutaraldehyde was added in an amount of 2wt.% based on the weight of microcrystalline cellulose to produce sample four.
Example 5:
this example provides another crosslinked esterified modified microcrystalline cellulose, which was prepared in substantially the same manner as in example 1, except that glyoxal was used as the crosslinking agent instead of glutaraldehyde to prepare sample five.
Example 6:
this example provides another crosslinked esterified modified microcrystalline cellulose, which was prepared in substantially the same manner as in example 5, except that glyoxal was added in an amount of 2wt.% based on the weight of microcrystalline cellulose to produce sample six.
Example 7:
the embodiment provides a crosslinked esterified modified microcrystalline cellulose, and the preparation method thereof specifically comprises the following steps:
preparation of microcrystalline cellulose: 200kg of wood pulp and 10wt.% of dilute sulfuric acid are mixed in a reaction kettle according to the mass ratio of 1:15, acidolysis is carried out for 1.5 hours in the temperature range of 95-100 ℃ to obtain acidolysis solution, the acidolysis solution is cooled to 65 ℃, 15wt.% of ammonia water is added into the acidolysis solution to adjust the pH value to 6.5, the neutralization solution is pumped into a plate-and-frame filter press for filter pressing, and then primary reverse osmosis water is added for washing until the electric conductivity of the washing solution is less than 200uS.cm -1 And pressing to dry to obtain a microcrystalline cellulose filter cake. And (3) sending the filter cake into a flash dryer to be dried at the air inlet temperature of 150-160 ℃ and the air outlet temperature of 80-90 ℃, collecting the dried material, and sieving with a 100-mesh ultrasonic sieve to obtain the microcrystalline cellulose.
Crosslinking modification: the microcrystalline cellulose prepared above was prepared into a 30wt.% suspension with pure water, and subjected to micronization treatment with a ball mill at a rotation speed of 500r/min for 60 minutes. Transferring the feed liquid into a crosslinking reaction kettle, adding glutaraldehyde accounting for 0.5wt.% of the weight of the microcrystalline cellulose, and stirring at 45 ℃ for reaction for 4 hours to obtain the crosslinked modified microcrystalline cellulose.
Esterification modification: adding soybean oil and ethanol mixed solution into the reaction kettle with the crosslinked modified microcrystalline cellulose, wherein the soybean oil accounts for 30wt.% of the weight of the microcrystalline cellulose, the ethanol accounts for 24wt.% of the weight of the microcrystalline cellulose, and uniformly stirring and reacting for 3 hours at the temperature of 135-140 ℃ to obtain reaction solution.
Spray drying: pumping the reaction liquid into a spray dryer to carry out spray drying under the conditions that the air inlet temperature is 170-180 ℃ and the air outlet temperature is 60-70 ℃. And collecting the sprayed and dried material, removing iron under 100000 gauss by an iron remover, sieving by a 100-mesh ultrasonic sieve after iron removal is finished, and sieving to obtain the crosslinked esterified modified microcrystalline cellulose which is sample seven.
Example 8:
this example provides another crosslinked esterified modified microcrystalline cellulose, prepared in substantially the same manner as in example 7, except that 10wt.% soybean oil and 8wt.% ethanol were added to the soybean oil ethanol blend to produce sample eight.
Example 9:
this example provides another crosslinked esterified modified microcrystalline cellulose, prepared in substantially the same manner as in example 7, except that the added soybean oil in the soybean oil ethanol blend was 50wt.% of the microcrystalline cellulose and the ethanol was 60wt.% of the microcrystalline cellulose, to produce sample nine.
Comparative example 1:
the comparative example provides a nanocellulose crystal, which is prepared by weighing 15g of microcrystalline cellulose powder, adding the microcrystalline cellulose powder into 140mL of 65wt.% sulfuric acid, mechanically stirring for 6 hours in a constant-temperature water bath at 45 ℃, adding a large amount of distilled water after the reaction is completed, stopping the reaction, cooling to room temperature, performing ultrasonic dispersion under the condition of 250W with the power of 45kHz, repeatedly dialyzing for three times by using pure water until the pH is stable, standing the dialyzed sample at 4 ℃ for overnight, and freeze-drying at-60 ℃ to obtain a white nanocellulose crystal, namely a sample ten.
Comparative example 2:
the comparative example provides a crosslinked modified microcrystalline cellulose prepared by taking a crosslinked modified microcrystalline cellulose reaction solution obtained by crosslinking modification in example 1, pumping the reaction solution into a spray dryer, and spray drying the reaction solution under the conditions that the air inlet temperature is 190-200 ℃ and the air outlet temperature is 80-90 ℃. Collecting the sprayed and dried material, removing iron under the condition of 80000 gauss by an iron remover, sieving by a 100-mesh ultrasonic sieve after iron removal is finished, and sieving to obtain crosslinked modified microcrystalline cellulose, which is sample eleven.
Comparative example 3:
the comparative example provides an esterified modified microcrystalline cellulose, which is prepared by taking microcrystalline cellulose prepared in the example 1, adding the microcrystalline cellulose and a soybean oil-ethanol mixed solution into a reaction kettle, wherein soybean oil accounts for 20wt.% of the weight of the microcrystalline cellulose in the soybean oil-ethanol mixed solution, ethanol accounts for 20wt.% of the weight of the microcrystalline cellulose, uniformly stirring, reacting for 4 hours at a temperature ranging from 110 ℃ to 115 ℃ to obtain an esterified modified microcrystalline cellulose reaction solution, pumping the esterified modified microcrystalline cellulose reaction solution into a spray dryer, and spray drying the reaction solution at an air inlet temperature ranging from 190 ℃ to 200 ℃ and an air outlet temperature ranging from 80 ℃ to 90 ℃. Collecting the sprayed and dried material, removing iron under the condition of 80000 gauss by an iron remover, sieving by a 100-mesh ultrasonic sieve after iron removal is finished, and sieving to obtain esterified modified microcrystalline cellulose, which is a sample twelve.
Example 10:
in this example, the samples provided in examples 1 to 9 and comparative examples 1 to 3 were used to prepare a collagen composite matrix, and the preparation method thereof was as follows: 1wt.% of acetic acid aqueous solution is used as a solvent to prepare a collagen solution with the concentration of 1wt.%, and 1wt.% of acetic acid aqueous solution is used as a solvent to prepare sample one to sample twelve solutions with the concentration of 1wt.% respectively for standby. And respectively dripping the sample solutions into a collagen solution, and mechanically stirring for 6 hours at room temperature to uniformly mix to obtain a collagen composite solution, wherein the collagen composite solution contains 5 parts by mass of the sample solution and 95 parts by mass of the collagen solution. And (3) defoaming the collagen composite solution in vacuum, injecting the defoamed collagen composite solution into a polytetrafluoroethylene mould for natural spreading, standing at 4 ℃ for 12 hours, and naturally drying at room temperature to obtain the collagen composite matrix.
Performance testing
The collagen composite matrix prepared in example 10 was subjected to a swelling property test and a mechanical property test, respectively.
Swelling property test:
at room temperature, the dried collagen composite matrix was weighed and recorded as W d Soaking in phosphate buffer solution for 20min, 60min, and 250min respectively, taking out sample, wiping to remove surface residual liquid, weighing wet mass, and recording as W t The sample swell ratio (SR%) at different immersion times was calculated using the following formula:
；
the average of 5 replicates was taken for each group and the results are shown in table 1.
Mechanical property test:
standardized strip samples (2 mm. Times.5 mm) were taken separately and tested for uniaxial stretching at room temperature at a constant stretching rate of 3mm/min, mainly characterizing three properties: tensile modulus, tensile strength elongation at break; the average of 5 replicates was taken for each group and the results are shown in table 1.
TABLE 1 Performance test
It is clear from Table 1 and examples 1 to 6 and comparative example 3 that the choice of the crosslinking agent in the crosslinking modification process has a certain influence on the crystallinity of microcrystalline cellulose and the mechanical properties of the collagen composite matrix. At present, glutaraldehyde is the most widely used dialdehyde crosslinking agent, but compared with glyoxal, three methylene groups still exist between two pairs of carbonyl groups of glutaraldehyde, and the glutaraldehyde crosslinking agent has a certain binding effect on crosslinked crosslinking points, so that the crystallinity of microcrystalline cellulose under the crosslinking effect of glutaraldehyde is slightly lower than that of microcrystalline cellulose crosslinked by glyoxal, and the mechanical strength and the stability of a space structure of a collagen composite matrix are further influenced. Meanwhile, when the addition amount of the cross-linking agent is 0.1-2 wt.% of microcrystalline cellulose, the prepared collagen composite matrix has better water absorption performance and mechanical property. It is apparent from the combination of Table 1, examples 7 to 9 and comparative example 2 that, when the amount of soybean oil added is 20 to 50wt.% of microcrystalline cellulose, further improvement of mechanical properties of microcrystalline cellulose is achieved by continuing the esterification modification on the basis of the crosslinking modification.
The above examples are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the protection scope of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the crosslinked esterified modified microcrystalline cellulose is characterized by comprising the following steps of:
s1, micronizing microcrystalline cellulose suspension, and adding a cross-linking agent for cross-linking reaction to obtain cross-linked modified microcrystalline cellulose;
s2, performing esterification reaction on the crosslinked modified microcrystalline cellulose prepared in the step S1 and soybean oil to prepare the crosslinked esterified modified microcrystalline cellulose.
2. The method of claim 1, wherein in step S1, the microcrystalline cellulose is present in the microcrystalline cellulose suspension at a concentration of 20 to 30wt%.
3. The method according to claim 2, wherein in step S1, the crosslinking agent is selected from one or two of glutaraldehyde and glyoxal.
4. A production method according to claim 3, wherein in step S1, the amount of the crosslinking agent added is 0.1 to 2wt.% of microcrystalline cellulose.
5. The preparation method according to claim 2, wherein in step S2, soybean oil is added in an amount of 20 to 50wt.% of microcrystalline cellulose by mass.
6. The preparation method according to claim 2, wherein in the step S2, the esterification reaction uses ethanol as a solvent, and the mass ratio of the soybean oil to the ethanol is 1 (0.8-1.2).
7. The method according to claim 2, wherein in step S2, the esterification reaction is carried out at a temperature of 100 to 150 ℃ for 3 to 4 hours.
8. The preparation method according to claim 2, wherein in step S2, after the esterification reaction, the obtained reaction solution is subjected to spray drying, iron removal and sieving to obtain the crosslinked esterified modified microcrystalline cellulose.
9. The crosslinked esterified modified microcrystalline cellulose produced by the process of any one of claims 1 to 8.
10. A collagen composite matrix comprising the crosslinked esterified modified microcrystalline cellulose of claim 9.
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