CN110483832B - Multi-characteristic natural rubber and agar composite mesoporous membrane and preparation method thereof - Google Patents
Multi-characteristic natural rubber and agar composite mesoporous membrane and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 22
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- JWGGSJFIGIGFSQ-UHFFFAOYSA-N N-dodecanoylglycine Chemical compound CCCCCCCCCCCC(=O)NCC(O)=O JWGGSJFIGIGFSQ-UHFFFAOYSA-N 0.000 claims description 4
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- FCBUGCHAVCFTHW-NTISSMGPSA-N sodium;(2s)-2-(tetradecanoylamino)pentanedioic acid Chemical compound [Na].CCCCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O FCBUGCHAVCFTHW-NTISSMGPSA-N 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
- QNAYBMKLOCPYGJ-UHFFFAOYSA-M alaninate Chemical compound CC(N)C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-M 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- WQZGKKKJIJFFOK-FPRJBGLDSA-N beta-D-galactose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-FPRJBGLDSA-N 0.000 description 1
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- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/12—Agar-agar; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/12—Agar-agar; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
- C08J2407/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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Abstract
The invention discloses a multi-characteristic natural rubber and agar composite mesoporous membrane and a preparation method thereof, and the specific method comprises the following steps: firstly, respectively treating a natural latex solution and an agar solution by using a high-shear homogeneous emulsification dispersion machine, then stabilizing the natural latex solution and the agar solution by using an amino acid surfactant, respectively adjusting the pH value to 10-11 by using an alkaline solution, then blending the natural latex-surfactant solution and the agar-surfactant solution, treating the mixed solution by using microwave irradiation for at least 3min, then pre-freezing the mixed solution in liquid nitrogen for 30min, and finally freeze-drying the mixed solution at-50 ℃ for at least 12h to obtain the natural rubber and agar composite mesoporous membrane. The method has the advantages of ingenious conception and simple process and operation, and the prepared natural rubber and agar composite membrane has a uniform mesoporous structure, has good moisture absorption performance, water locking performance, air permeability, tensile stress strain performance and flexibility, can be used as a wound dressing and a base material for loading medicaments, and has a wide application range.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a multi-characteristic natural rubber and agar composite mesoporous membrane and a preparation method thereof.
Background
Agar is a polysaccharide extracted from seaweed, and is a hydrophilic colloid mainly comprising agarose, is insoluble in cold water, melts when heated to 95 deg.C in water, can absorb 20 times of water, solidifies at a temperature below 40 deg.C, and forms stable gel when the concentration is as low as 1%. At present, agar is widely used as a gelling agent in the fields of foods and microbial culture. However, the single agar membrane is brittle and has poor ductility, which limits its application in the medical field.
Natural latex is a viscous milky white liquid, and the main component of the natural latex is cis-1, 4-polyisoprene rubber particles. The natural rubber particles have hydrophobic property, and form stable rubber-water-based dispersion system by adsorbing lipid compounds such as protein and phospholipid on the surfaces in solution. At normal temperature, the natural rubber has excellent elasticity, film forming performance, mechanical property and flexibility. At present, natural rubber is widely used as a protective material for gloves and condoms. However, the single natural rubber membrane has strong hydrophobicity and high compactness, and has poor air permeability and water vapor permeability, so that the application of the single natural rubber membrane in the medical field is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a multi-characteristic natural rubber and agar composite mesoporous membrane and the natural rubber and agar composite mesoporous membrane prepared by the method, aiming at the problems of a single natural rubber material and an agar material.
To achieve the object of the present invention, the present inventors have searched for the blending characteristics of natural latex and agar solution based on the disclosed method for preparing a natural rubber membrane or agar membrane, and have found that rubber particles are rapidly flocculated out after adding agar solution to natural latex, and thus cannot be directly blended. In order to promote the coexistence of natural latex and agar solution, the present inventors have intensively studied the composition characteristics and dispersion stability characteristics of natural latex and agar solution. Since the isoelectric point pI of the natural latex protein is between pH4 and 5 (Perussa protein and rubber particle protective layer. tropical agricultural science, 1985, (1): 22-27.), in a high ammonia alkaline environment, dissociated latex protein carries negative charges and is adsorbed on the surface of rubber particles through van der Waals force to form a protective structure of the outermost layer of the rubber particles, which is the main reason for the stability of the natural latex. Because agarose is a non-ionic polysaccharide and has the basic structure of long chains formed by alternately connecting 1, 3-linked beta-D-galactose and 1, 4-linked 3, 6-lacto-L-galactose, the agarose can form strong hydrogen bond interaction with latex proteins. When the agar solution is added to a natural latex at normal temperature, the added agar solution rapidly coagulates due to a rapid decrease in temperature, so that latex proteins interacting with agarose in the agar easily peel off from the surface of rubber particles, resulting in a decrease in the number of charges on the surface of the rubber particles, and deterioration in the dispersion stability of the natural latex, which is manifested by flocculation and precipitation of the rubber particles. In order to solve the problem of rubber particle flocculation in the blending process of natural latex and agar solution, the inventor explores a method for pretreating the natural latex solution or agar solution by using a high-shear homogeneous emulsification dispersion machine, stabilizing the natural latex solution or agar solution by using an amino acid surfactant respectively, and blending the natural latex-surfactant solution and the agar-surfactant solution, and finally finds that the process combination can ensure the uniform blending of the natural latex and the agar solution at normal temperature and can stably exist for a long time.
Because the rubber particles and the agarose have different molecular sizes and structures, the difference of the flow properties of the rubber particles and the agarose is large in the process of forming a film by using a natural latex and agar blending solution, so that the phenomenon of obviously separating the rubber particles and the agar molecules in a natural rubber and agar composite film is caused, and the composition of substances at different positions in the film is not uniform. In order to solve the problem, the inventor further explores a method of rapidly cooling by using liquid nitrogen and freeze-drying at low temperature after treating a mixed solution of a natural latex-surfactant solution and an agar-surfactant solution by using microwave irradiation, and finally discovers that the process combination can ensure that the natural rubber and agar composite membrane has complete shape and uniform aperture size, and rubber particles and agar molecules in the membrane are uniformly distributed in a staggered manner.
The multi-characteristic natural rubber and agar composite mesoporous membrane provided by the invention is characterized in that the mass ratio of natural rubber particles to agar in the mesoporous membrane is 1: 1-10: 1, the content of amino acid surfactant in each gram of mesoporous membrane is at least 161mg, the pore size distribution of the mesoporous membrane is 10-50 nm, the porosity in the membrane is more than or equal to 55.0%, the moisture absorption capacity of each gram of mesoporous membrane is more than or equal to 8.9g, the water locking performance value of the membrane is less than or equal to 8.5cm, and the water evaporation capacity of the membrane is more than or equal to 6.9g.h-1.cm-2The tensile strength of the film is more than or equal to 5.7MPa, the breaking elongation of the film is more than or equal to 473%, and the softness value of the film is less than or equal to 185 mN.
In order to solve the technical problems, the technical scheme of the invention is as follows: the preparation method of the multi-characteristic natural rubber and agar composite mesoporous membrane comprises the following process steps and conditions:
1) preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and stirring speed of 20r/min, treating the natural latex solution for 10-20 min by using a high-shear homogeneous emulsification dispersion machine under the condition of stirring speed of 3000-4000 r/min, then adding 20-30 g of amino acid surfactant under the condition of stirring speed of 2000-3000 r/min, and adjusting the pH value of the natural latex-surfactant solution to 10-11 by using an alkaline solution;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 20-40 g of agar under the conditions of keeping the solution boiling and stirring rotation speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 10-20 min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring rotation speed of 8000-12000 r/min, then adding 20-30 g of amino acid surfactant under the conditions of stirring rotation speed of 2000-3000 r/min, and adjusting the pH value of the agar-surfactant solution to 10-11 by using an alkaline solution;
3) preparing a natural rubber and agar composite mesoporous membrane: mixing the natural rubber latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1: 2-1: 10 for 20min under the condition that the stirring speed is 2000-3000 r/min, then performing microwave irradiation treatment for at least 3min with the frequency of 2450MHz and the power of 1-2 kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally performing freeze drying on the mixed solution at-50 ℃ for at least 12h to obtain the multi-characteristic natural rubber and agar composite mesoporous membrane.
The preparation method of the multi-characteristic natural rubber and agar composite mesoporous membrane is characterized in that the amino acid surfactant in the step 1) and the step 2) is at least one of glutamic acid series, glycine series and alanine series.
The preparation method of the multi-characteristic natural rubber and agar composite mesoporous membrane is characterized in that in the step 1) and the step 2), the amino acid surfactant is at least one of myristoyl glutamic acid, myristoyl sodium glutamate, lauroyl glycine, potassium cocoyl glycine, N-octanoyl glycine, sodium lauroyl alanine, potassium lauroyl alanine and sodium N-coconut oil fatty acid-L-alanine.
According to the preparation technical scheme of the multi-characteristic natural rubber and agar composite mesoporous membrane, the amino acid surfactant with foaming property and salt resistance is skillfully utilized, firstly, the characteristic that the amino acid surfactant can form micelles is utilized, and agar molecules or aggregates, natural rubber particles or micelles which are treated by a high-shear homogeneous emulsification dispersion machine are respectively encapsulated and wrapped so as to promote the uniform mixing of latex and agar; secondly, the charge quantity absorbed on the surface of the rubber particle is supplemented by utilizing the property that the amino group and the carboxyl group in the amino acid surfactant have charges after dissociation, so that the problems of reduction of the charge quantity on the surface of the rubber particle and deterioration of stability in the blending process of natural latex and agar are solved, the stable coexistence of the natural latex and the agar is ensured, and a uniform solution is provided for the preparation of the natural rubber and agar composite membrane; then, by utilizing the rapid freezing action of ultralow-temperature liquid nitrogen, fine ice crystals are formed in the natural latex and agar blending solution so as to promote the sublimation of the ice crystals to form a mesoporous structure in the subsequent freeze drying process; and finally, by utilizing the action principle that the amino acid surfactant can reduce the surface tension of the solution, the protective action of the surfactant on rubber particles and agar molecules in the freeze drying process is realized, so that the integrity of the appearance form and the uniformity of the microcosmic composition of the natural rubber and agar composite mesoporous membrane after freeze drying are maintained.
The invention also has the following advantages:
1. the method provided by the invention has the advantages of ingenious conception and simple process and operation, and the main equipment used is a stirring device, a high-shear homogenizing emulsifying disperser and a microwave processor which are common laboratory equipment without additional investment.
2. The natural rubber and agar composite mesoporous membrane prepared by the method integrates the advantages of natural rubber and agar, so that the mesoporous membrane has good mechanical property, water absorption, water locking property and air permeability, can be used as a wound dressing and a base material for loading medicaments, and has a wide application range, and thus, the natural rubber and agar composite mesoporous membrane has a good market prospect.
3. The natural latex, agar and amino acid surfactant used in the method provided by the invention are conventional chemical materials and come from natural plants or further processed products, so that the materials are wide in source, green and safe.
Detailed Description
The following examples are given to illustrate the present invention in more detail, and it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that the insubstantial modifications and variations of the present invention can be made by those skilled in the art based on the above disclosure.
Example 1
1) Preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and stirring speed of 20r/min, then treating the natural latex solution for 20min by using a high-shear homogeneous emulsification dispersion machine under the condition of stirring speed of 3000r/min, then adding 20g of sodium myristoyl glutamate surfactant under the condition of stirring speed of 3000r/min, and then adjusting the pH value of the natural latex-surfactant solution to 10 by using 10% by mass of an ammonia water solution;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 20g of agar under the conditions of keeping the solution boiling and stirring speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 10min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring speed of 8000r/min, then adding 20g of sodium myristoyl glutamate surfactant under the condition of stirring speed of 2000r/min, and adjusting the pH value of the agar-surfactant solution to 10 by using an ammonia water solution with the mass fraction of 10%;
3) preparing a natural rubber and agar composite mesoporous membrane: under the condition that the stirring speed is 2000r/min, mixing the natural latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1:2 for 20min, then irradiating the mixture for 3min by using microwave with the frequency of 2450MHz and the power of 1kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally freeze-drying the mixed solution at the temperature of 50 ℃ below zero for 12h to obtain the natural rubber and agar composite mesoporous membrane with multiple characteristics. The mass ratio of the natural rubber particles to the agar in the membrane is 10:1, and the content of the amino acid surfactant in each gram of the membrane is 161 mg.
Example 2
1) Preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and stirring speed of 20r/min, then treating the natural latex solution for 10min by using a high-shear homogeneous emulsification dispersion machine under the condition of stirring speed of 4000r/min, then adding 15g of lauroyl glycine and 10g of potassium cocoyl glycinate surfactant under the condition of stirring speed of 2000r/min, and then adjusting the pH value of the natural latex-surfactant solution to 11 by using an ammonia water solution with the mass fraction of 5%;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 40g of agar under the conditions of keeping the solution boiling and stirring speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 20min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring speed of 12000r/min, then adding 15g of n-octanoyl glycine and 15g of sodium lauroyl alanine surfactant under the condition of stirring speed of 3000r/min, and adjusting the pH value of the agar-surfactant solution to 11 by using an ammonia water solution with the mass fraction of 5%;
3) preparing a natural rubber and agar composite mesoporous membrane: under the condition that the stirring speed is 3000r/min, mixing the natural latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1:10 for 20min, then irradiating for 6min by using microwave with the frequency of 2450MHz and the power of 2kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally freeze-drying the mixed solution at-50 ℃ for 16h to obtain the natural rubber and agar composite mesoporous membrane with multiple characteristics. The mass ratio of the natural rubber particles to the agar in the membrane is 1:1, and the content of the amino acid surfactant in each gram of the membrane is 307 mg.
Example 3
1) Preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and 20r/min of stirring speed, treating the natural latex solution for 15min by using a high-shear homogeneous emulsification dispersion machine under the condition of 3500r/min of stirring speed, then adding 14g of n-octanoyl glycine and 14g of sodium lauroyl alanine surfactant under the condition of 2500r/min of stirring speed, and adjusting the pH value of the natural latex-surfactant solution to 10.5 by using a sodium hydroxide solution with the mass fraction of 1%;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 30g of agar under the conditions of keeping the solution boiling and stirring speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 16min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring speed of 10000r/min, then adding 15g of lauroyl glycine and 10g of potassium cocoyl glycinate surfactant under the condition of stirring speed of 2300r/min, and adjusting the pH value of the agar-surfactant solution to 10.5 by using a sodium hydroxide solution with the mass fraction of 1%;
3) preparing a natural rubber and agar composite mesoporous membrane: under the condition of stirring rotation speed of 2500r/min, mixing the natural latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1:5 for 20min, then irradiating with microwave with the frequency of 2450MHz and the power of 1.8kW for 5min, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally freeze-drying the mixed solution at-50 ℃ for 15h to obtain the multi-characteristic natural rubber and agar composite mesoporous membrane. The mass ratio of the natural rubber particles to the agar in the membrane was 2.7:1, and the content of the amino acid surfactant per gram of the membrane was 254 mg.
Example 4
1) Preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and 20r/min of stirring speed, treating the natural latex solution for 13min by using a high-shear homogeneous emulsifying dispersion machine under the condition of 3800r/min of stirring speed, then adding 10g of potassium lauroyl alanine and 20g of N-coconut oil fatty acid-L-sodium alanine surfactant under the condition of 2200r/min of stirring speed, and adjusting the pH value of the natural latex-surfactant solution to 10.5 by using a sodium hydroxide solution with the mass fraction of 2%;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 25g of agar under the conditions of keeping the solution boiling and stirring speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 14min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring speed of 9000r/min, then adding 10g of potassium lauroyl alaninate and 16g of N-coconut oil fatty acid-L-sodium alaninate surfactant under the condition of stirring speed of 2600r/min, and adjusting the pH value of the agar-surfactant solution to 10.5 by using a sodium hydroxide solution with the mass fraction of 2%;
3) preparing a natural rubber and agar composite mesoporous membrane: mixing the natural latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1:4 for 20min under the condition of stirring rotation speed of 2800r/min, then carrying out microwave irradiation treatment for 4min with the frequency of 2450MHz and the power of 1.5kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally carrying out freeze drying on the mixed solution for 14h at the temperature of 50 ℃ below zero to obtain the multi-characteristic natural rubber and agar composite mesoporous membrane. The mass ratio of the natural rubber particles to the agar in the membrane is 4:1, and the content of the amino acid surfactant in each gram of the membrane is 255 mg.
Example 5
1) Preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and 20r/min of stirring speed, treating the natural latex solution for 18min by using a high-shear homogeneous emulsifying dispersion machine under the condition of 3300r/min of stirring speed, then adding 13g of n-octanoyl glycine and 10g of myristoyl glutamic acid surfactant under the condition of 2400r/min of stirring speed, and adjusting the pH value of the natural latex-surfactant solution to 10.5 by using an ammonia water solution with the mass fraction of 5%;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 35g of agar under the conditions of keeping the solution boiling and stirring speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 18min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring speed of 11000r/min, then adding 14g of n-octanoyl glycine and 14g of myristoyl glutamic acid surfactant under the condition of stirring speed of 2700r/min, and adjusting the pH value of the agar-surfactant solution to 10.5 by using an ammonia water solution with the mass fraction of 5%;
3) preparing a natural rubber and agar composite mesoporous membrane: under the condition that the stirring speed is 2300r/min, mixing the natural latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1:3 for 20min, then irradiating for 3min by using microwave with the frequency of 2450MHz and the power of 1.2kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally freeze-drying the mixed solution at-50 ℃ for 13h to obtain the multi-characteristic natural rubber and agar composite mesoporous membrane. The mass ratio of the natural rubber particles to the agar in the membrane was 3.8:1, and the content of the amino acid surfactant per gram of the membrane was 210 mg.
In order to examine the characteristics of the natural rubber and agar composite films of the present invention, the natural rubber and agar composite films prepared in the above examples were randomly selected, and the measured properties are shown in table 1. And (3) measuring the pore size distribution condition in the film by using a scanning electron microscope, wherein the pore size distribution in all the films is 10-50 nm and belongs to the size of mesopores. The porosity of the membrane (Liuwenhui, Liudaoya, Chengming, etc. chitosan-based biomedical materials and application research progress thereof, functional polymers report 2001, 14(4): 493 and 496.) is determined by adopting a liquid substitution method, and the larger the value of the porosity, the more the pore structure in the membrane is. The porosity of all the membranes is more than or equal to 55.0 percent, which indicates that the natural rubber and agar composite membrane has a good porous loose structure. The moisture absorption performance of the film is measured by adopting a gravimetric method, and the higher the value of the moisture absorption amount is, the better the moisture absorption performance of the film is. The moisture absorption value of all the films is more than or equal to 8.9g of water-1The membrane shows that the natural rubber and agar composite membrane has good moisture absorption performance. The water-locking performance of the film is measured by adopting a diffusion method (spring in summer, yellow luck, bright and the like. the air permeability, water absorption and water-locking performance of two different foam dressings are compared, Chinese primary medicine 2017, 24(13): 1946-1949.), and the lower the value of the diffusion diameter is, the better the water-locking performance of the film is. The diffusion diameter values of all the membranes are less than or equal to 8.5cm, which shows that the natural rubber and agar composite membrane has good water locking performance. The air permeability of the film was evaluated by measuring the amount of water evaporation (bright, sumicin, li, etc.. the effect of different dressing combinations on the wound microenvironment in donor areas of burn patients, china journal of burn, 2009, 25(3):218 deg. 221 deg.) a greater value for water evaporation indicates a better gas permeability of the membrane. The water evaporation capacity value of all the membranes is more than or equal to 6.9g.h-1.cm-2The natural rubber and agar composite membrane has good air permeability. The tensile strength and elongation at break of the film were determined according to GB/T528-2009 standard. The tensile strength of all the membranes is more than or equal to 5.7MPa, and the elongation at break is more than or equal to 473%, which shows that the natural rubber and agar composite membrane has good tensile stress strain performance. The softness of the films was measured according to GB/T8942-2016, with lower values indicating better softness of the films. The softness values of all the membranes are less than or equal to 185mN, which shows that the natural rubber and agar composite membrane has good softness.
TABLE 1 characteristics of natural rubber and agar composite mesoporous membranes
Claims (2)
1. A multi-characteristic natural rubber and agar composite mesoporous membrane is characterized in that: the mass ratio of the natural rubber particles to the agar in the mesoporous membrane is 1: 1-10: 1, the amino acid surfactant in each gram of the mesoporous membrane is at least 161mg, the pore size distribution of the mesoporous membrane is 10-50 nm, the porosity in the membrane is more than or equal to 55.0%, the moisture absorption of each gram of the mesoporous membrane is more than or equal to 8.9g, the water locking performance value of the mesoporous membrane is less than or equal to 8.5cm, and the water evaporation capacity of the mesoporous membrane is more than or equal to 6.9g.h-1.cm-2The tensile strength of the film is more than or equal to 5.7MPa, the elongation at break of the film is more than or equal to 473%, and the softness value of the film is less than or equal to 185 mN; the amino acid surfactant is one of myristoyl sodium glutamate, lauroyl glycine, potassium cocoyl glycinate, N-octanoyl glycine, sodium lauroyl alanine, potassium lauroyl alanine, sodium N-coconut oil fatty acid-L-alanine, and myristoyl glutamic acid.
2. A method for preparing the multi-property natural rubber and agar composite mesoporous membrane as claimed in claim 1, which comprises the following steps and conditions:
1) preparation of natural latex-surfactant solution: adding 150g of distilled water into 300g of natural latex under the conditions of 20 ℃ and stirring speed of 20r/min, treating the natural latex solution for 10-20 min by using a high-shear homogeneous emulsification dispersion machine under the condition of stirring speed of 3000-4000 r/min, then adding 20-30 g of amino acid surfactant under the condition of stirring speed of 2000-3000 r/min, and adjusting the pH value of the natural latex-surfactant solution to 10-11 by using an alkaline solution;
2) preparation of agar-surfactant solution: boiling 1000mL of distilled water, adding 20-40 g of agar under the conditions of keeping the solution boiling and stirring rotation speed of 20r/min, continuously keeping the solution boiling for 30min, treating the agar solution for 10-20 min by using a high-shear homogeneous emulsification dispersion machine under the conditions of 50 ℃ and stirring rotation speed of 8000-12000 r/min, then adding 20-30 g of amino acid surfactant under the conditions of stirring rotation speed of 2000-3000 r/min, and adjusting the pH value of the agar-surfactant solution to 10-11 by using an alkaline solution;
3) preparing a natural rubber and agar composite mesoporous membrane: mixing the natural rubber latex-surfactant solution and the agar-surfactant solution according to the mass ratio of 1: 2-1: 10 for 20min under the condition that the stirring speed is 2000-3000 r/min, then performing microwave irradiation treatment for at least 3min with the frequency of 2450MHz and the power of 1-2 kW, then quickly pre-freezing the mixed solution in liquid nitrogen for 30min, and finally performing freeze drying on the mixed solution at-50 ℃ for at least 12h to obtain the multi-characteristic natural rubber and agar composite mesoporous membrane.
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| CN1116085A (en) * | 1993-02-12 | 1996-02-07 | 菲迪亚高级生物聚合物公司 | Multilayer nonwoven tissue containing a surface layer comprising at least one hyaluronic acid ester |
| CN102256694A (en) * | 2008-12-17 | 2011-11-23 | 花王株式会社 | Method for producing hydrogel particles |
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| CN102256694A (en) * | 2008-12-17 | 2011-11-23 | 花王株式会社 | Method for producing hydrogel particles |
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