CN106675019A - Preparation method of aramid 1313/chitosan macroporous composite membrane material - Google Patents
Preparation method of aramid 1313/chitosan macroporous composite membrane material Download PDFInfo
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- CN106675019A CN106675019A CN201611180821.3A CN201611180821A CN106675019A CN 106675019 A CN106675019 A CN 106675019A CN 201611180821 A CN201611180821 A CN 201611180821A CN 106675019 A CN106675019 A CN 106675019A
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- Prior art keywords
- aramid fiber
- shitosan
- chitosan
- aramid
- composite membrane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a simple preparation method of an aramid 1313/chitosan macroporous composite membrane material. Homogeneous aramid 1313 and a DMSO solution of chitosan are firstly subjected to hybrid reaction for coating to prepare a composite membrane material; the chitosan in the composite membrane material is degraded by using a biological enzyme; and the aramid 1313/chitosan macroporous composite membrane material is finally obtained. The preparation method is simple and is environment-friendly in process, and the air permeability, moisture permeability, water absorption capability and antibacterial property of the obtained macroporous material are greatly improved in comparison with those of a pure aramid membrane.
Description
Technical field
The present invention relates to the preparation method and its obtained product of aramid fiber 1313/shitosan macropore composite film material.
Background technology
Aramid fiber 1313, full name " poly "（MPIA）Fiber, is by m-phthaloyl chloride and isophthalic
The organic polymer fiber of diamines synthesis.Aramid fiber 1313 has excellent high temperature resistant and fire resistance, good spinnability and chi
Very little stability and preferable mechanical performance, are ripe current Technical comparing, the most widely used inherent fire-retardant fiber.Disappearing
Good application has been obtained in anti-clothes, military uniform and bedding material.
Traditional textile is microorganism attachment, breeding and the good medium propagated.With the development of textile science technology with
And the requirement of new period clothing function, people can not have been met to fabric breathability, penetrability, water imbibition and antibiotic property
It is required that, therefore, develop the study hotspot that the textile of function admirable turns into industry.Shitosan is rich content in nature
Natural polymer, it is the product that chitin removes most of acetyl group, with nontoxic, pollution-free, degradable etc. excellent
Point, and amino in molecule again can and the anion binding of bacterial cell wall surface hinder its biosynthesis so as to play antibacterial
Effect.Additionally, contain substantial amounts of amino and hydroxyl in its molecule, and can be compatible with many macromolecular compounds, this is using blending
The composite film material that legal system obtains aramid fiber 1313/shitosan provides theoretical foundation.
2013, the Sam Soo Kim team of Japan used dimethyl sulfoxide (DMSO) first（DMSO）It is solvent, respectively to aramid fiber
1313 and dissolved into the shitosan after salt, then blending has synthesized the composite film material of aramid fiber 1313/shitosan, antibiotic property
Result test is satisfactory.However, the performance such as the gas permeability of its composite film material, penetrability and water imbibition does not have significantly changing
It is kind.So far, document and patent report related to this are also had no both at home and abroad.
The content of the invention
This problem uses enzyme biodegrading process first, aramid fiber 1313/shitosan is first synthesized by the way of solution blending and is combined
Membrane material, is then degraded using biology enzyme to the shitosan in composite membrane, finally gives having for natural macromolecular pore
The composite film material of the aramid fiber/shitosan of macroporous structure.The macropore composite film material of gained compared with former pure aramid fiber film, with good
Gas permeability well, penetrability, water imbibition and anti-microbial property.The purpose of the present invention can be reached by following measure：(1) by virtue
Synthetic fibre 1313 and dissolved with DMSO respectively into the shitosan crystal after salt, two kinds of solution are pressed after different proportion is mixed and is made
Film.(2) made composite membrane is put into the NaAc_HAc buffer solution containing biology enzyme, keeps uniform temperature and pH value,
Taken out after concussion a few hours, washing there can be the aramid fiber 1313/chitosan complex film material of macroporous structure after drying.The present invention
Have the following advantages that：The method degraded using enzyme first has been obtained the aramid fiber 1313 with macroporous structure/chitosan complex film material
Material, compared with pure aramid fiber film, its gas permeability, penetrability, water imbibition and anti-microbial property obtain larger raising；Synthesis technique is simple,
Reaction condition is gentle, and the time is short, easy to control；Using enzyme biodegrading process, environmental protection, efficiency high.
Specific embodiment
The purpose of invention can also be realized by following concrete measure：
Embodiment 1：
Aramid fiber 1313 uses distilled water, ethanol and acetone repeated washing twice successively, drying overnight under environment temperature.Take 10g dryings
Aramid fiber 1313 afterwards is placed in the there-necked flask of 250ml, adds 8g lithium chlorides, and 100ml DMSO solutions are stirred 6 hours at 130 DEG C,
Obtain the DMSO solution of the aramid fiber 1313 that concentration is 10%.
9g Chitosan powders are dissolved into the distilled water that 600ml contains 6g methanesulfonic acids, stirred at ambient temperature 24 hours
Afterwards, freeze-drying 48 hours, obtain shitosan mesylate crystals.Above-mentioned crystal 10g is taken in the there-necked flask of 250ml, is added
100ml DMSO solutions, stir 24 hours at room temperature, obtain the shitosan DMSO solution that concentration is 10%.
The DMSO solution of aramid fiber 1313 and shitosan in mass ratio 1/0.33 mixes, and mixed liquor is stirred under conditions of 60 DEG C
2 hours, with wet film maker film on a glass.After institute's film forming is soaked 6 hours in 1% sodium hydroxide solution, enough steamings are used
Distilled water is washed, and is then soaked respectively in room temperature distilled water and 80 DEG C of distilled water 6 hours and 20 minutes, and virtue is obtained after drying
The chitosan complex film of synthetic fibre 1313/.
0.1g composite membranes are taken in conical flask, adds the NaAc_HAc buffer solution and 0.2g shells of 50ml pH=5.5 poly-
Carbohydrase, vibrates 4 hours at 37 DEG C.Product after degraded can obtain aramid fiber 1313/shitosan macropore after distilling water washing, drying and answer
Membrane material is closed, labeled as composite membrane -1, its performance parameter is shown in Table 1.
Embodiment 2：
Concentration is the preparation of the DMSO solution of 10% aramid fiber 1313 and shitosan with embodiment 1.Aramid fiber 1313 and shitosan
DMSO solution in mass ratio 1/1 mixes, and mixed liquor stirs 2 hours under conditions of 60 DEG C, with wet film maker on a glass
Film.Institute's film forming in 1% sodium hydroxide solution after immersion 6 hours, with enough distillation water washings, then in room temperature distilled water and
Soaked respectively in 80 DEG C of distilled water 6 hours and 20 minutes, aramid fiber 1313/chitosan complex film is obtained after drying.
0.1g composite membranes are taken in conical flask, adds the NaAc_HAc buffer solution and 0.05g of 50ml pH=5.5 fine
The plain enzyme of dimension, vibrates 4 hours at 35 DEG C.Product after degraded can obtain aramid fiber 1313/shitosan macropore after distilling water washing, drying
Composite film material, labeled as composite membrane -2, its performance parameter is shown in Table 1.
Table 1
| Sample | Air penetrability（mm/s） | Vapor transfer rate（g/m2.24h） | Water absorbent rate（g/g） | Escherichia coli bacteriostasis rate（%） | Staphylococcus aureus bacteriostasis rate（%） |
| Pure aramid fiber film | 0.614 | 4671.15 | 3.73 | 0 | 0 |
| Composite membrane -1 | 17.25 | 5282.65 | 11.28 | 62.72 | 57.33 |
| Composite membrane -2 | 19.17 | 5571.41 | 8.92 | 61.38 | 59.64 |
Claims (1)
1. the preparation method of a kind of aramid fiber 1313/shitosan macropore composite film material, it is characterised in that the preparation method is by as follows
Two step compositions：
（1）By finite concentration aramid fiber 1313 and the homogeneous DMSO solution of shitosan, masking after mixing by a certain percentage；
（2）Gained film is put into the NaAc_HAc buffer solution containing biology enzyme, in concussion under uniform temperature and pH value condition
Taken out after certain hour, aramid fiber 1313/shitosan macropore composite film material obtained after washing, drying,
Wherein：In the step (1), the concentration of the DMSO solution of aramid fiber 1313 and shitosan is 1% ~ 15%, reaction temperature is 25 ~
150 DEG C, the reaction time is 4 ~ 24h, and aramid fiber 1313 and chitosan solution mass ratio are 1：（0.1~2）；The step（2）In, institute
It is cellulase or amylase or chitosan enzyme or papain with biology enzyme, cushioning liquid solution ph is 3.5 ~ 6.5, instead
It is 25 ~ 50 °C to answer temperature, and the reaction time is 2 ~ 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611180821.3A CN106675019A (en) | 2016-12-20 | 2016-12-20 | Preparation method of aramid 1313/chitosan macroporous composite membrane material |
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|---|---|---|---|
| CN201611180821.3A CN106675019A (en) | 2016-12-20 | 2016-12-20 | Preparation method of aramid 1313/chitosan macroporous composite membrane material |
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| CN106675019A true CN106675019A (en) | 2017-05-17 |
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| CN201611180821.3A Pending CN106675019A (en) | 2016-12-20 | 2016-12-20 | Preparation method of aramid 1313/chitosan macroporous composite membrane material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317367A (en) * | 2019-07-22 | 2019-10-11 | 陕西科技大学 | A kind of preparation method of chitosan/aramid nano-fiber laminated film |
| WO2022028244A1 (en) * | 2020-08-04 | 2022-02-10 | 宁波迪创医疗科技有限公司 | Tissue filling material, preparation method therefor, tissue engineering scaffold and use |
| CN116082744A (en) * | 2023-03-15 | 2023-05-09 | 河北立亚包装科技有限公司 | Antibacterial biodegradable preservative film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817932A (en) * | 2010-03-11 | 2010-09-01 | 南开大学 | Polyamido-amine dendrimers -modified macroporous crosslinked chitosan microsphere and preparation method thereof |
-
2016
- 2016-12-20 CN CN201611180821.3A patent/CN106675019A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817932A (en) * | 2010-03-11 | 2010-09-01 | 南开大学 | Polyamido-amine dendrimers -modified macroporous crosslinked chitosan microsphere and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SAM SOO KIM ET.AL: ""Miscibility and Antimicrobial Properties of m-Aramid/Chitosan Hybrid Composite"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| 张传凤等: ""壳聚糖制孔芳纶多孔膜材料的制备与表征"", 《中国化学会第18届反应性高分子学术研讨会论文集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317367A (en) * | 2019-07-22 | 2019-10-11 | 陕西科技大学 | A kind of preparation method of chitosan/aramid nano-fiber laminated film |
| WO2022028244A1 (en) * | 2020-08-04 | 2022-02-10 | 宁波迪创医疗科技有限公司 | Tissue filling material, preparation method therefor, tissue engineering scaffold and use |
| CN116082744A (en) * | 2023-03-15 | 2023-05-09 | 河北立亚包装科技有限公司 | Antibacterial biodegradable preservative film and preparation method thereof |
| CN116082744B (en) * | 2023-03-15 | 2023-09-19 | 河北立亚包装科技有限公司 | Antibacterial biodegradable preservative film and preparation method thereof |
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| RJ01 | Rejection of invention patent application after publication |
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