CN100344808C - Method for preparing hydrolytic polyacrylonitrilel soybean protein intelligent gel fiber - Google Patents
Method for preparing hydrolytic polyacrylonitrilel soybean protein intelligent gel fiber Download PDFInfo
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- CN100344808C CN100344808C CNB2006100259990A CN200610025999A CN100344808C CN 100344808 C CN100344808 C CN 100344808C CN B2006100259990 A CNB2006100259990 A CN B2006100259990A CN 200610025999 A CN200610025999 A CN 200610025999A CN 100344808 C CN100344808 C CN 100344808C
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Abstract
The present invention discloses a method for preparing a hydrolytic polyacrylonitrilel and soybean protein intelligent gel fiber, which comprises the following steps: a spinning dope is prepared; a coagulation bath is prepared; a saturated sodium sulfate water solution is prepared under the temperature of 25 DEG C, a glutaric dialdehyde water solution with concentration of 30 percent is added in the saturated sodium sulfate water solution according to volumetric proportion of 1 to 100, and then a concentrated sulfuric acid is added in the saturated sodium sulfate water solution to make the content of the sulfuric acid in the coagulation bath be from 1mol/L to 2mol/L; the prepared spinning dope is shaped by spinning in the coagulation bath under the temperature of 20 DEG C to 25 DEG C, and strand silks obtained are put in the coagulation bath under constant temperature for 10 hours to 15 hours for crosslinking; then the strand silks are drawn and dried in the air, and finally the hydrolytic polyacrylonitrilel and soybean protein intelligent gel fiber is prepared. The present invention has the advantage that the intelligent gel fiber obtained also has fast pH response speed besides certain biocompatibility; in addition, the shrinking degree of the present invention is from 30 percent to 50 percent and the shrinking force thereof approaches to 8kg/cm< 2 >, both of the shrinking degree and the shrinking force approach to the corresponding numerical value of human skeleton muscles.
Description
Technical field
The present invention relates to biological intelligence material technology field intelligent gel fiber preparation method, the preparation method who particularly relates to a kind of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre utilizes boiomacromolecule to have the method for the intelligent gel fiber of specific response for raw material by the wet spinning technology preparation.
Background technology
Aquogel is the multicomponent system that a kind of polymer three-dimensional network and water are formed, and can in water or some other aqueous solution swelling take place.When being in solvent swelling state, aquogel is soft and flexible, is similar to very much biological tissue.Studied the transition phenomenon mutually of gel rubber system since Flory, Kachalsky, Tanaka and other scientific theory and sample plot after, the research of intelligent gel just more and more receives publicity.So-called intelligent gel is meant and has the gel that can change and carry out reversible response accordingly to the variation (as temperature, pH value, electric field, light, solvent etc.) of environmental condition.Its Application Areas is quite extensive, as chemical valve, power chemistry brake, useful for drug delivery, circulation absorption, solute separation, bioreactor, bioassay, artificial-muscle and display system etc.Wherein, the research as artificial organs or artificial-muscle becomes current focus just gradually.When people often wish the recovery of physical function owing to being subjected to somatic damage and suffering disability, just need comprise that the help of the man-made organ of artificial-muscle recovers daily life.In these intelligent gels, the pH responsive gel is widely studied, gelatinous fibre especially, and reversible elongation and shrinkage phenomenon can take place in it under the pH environment that alternately changes, and this behavior is very similar to the characteristic that natural muscle shrinks.In fact just made gelatinous fibre as far back as nineteen fifty W.Kuhn and A.Katchalsky, but that this fiber disadvantage is its response speed is too slow, is a minute level with pH response.1985 between nineteen ninety-five, a large amount of new gel rubber systems have appearred, one of them more successful example is that polyacrylonitrile fibre is made pH responsive gel fiber through pre-oxidation and hydrolysis process.This fibrid and natural muscle are relatively listed in the table 1 some aspect of performances, can see that this fibrid is being better than natural muscle aspect degree of shrinkage and the convergent force, but also there is a big difference aspect response speed, fibre diameter.
The pH responsive gel fiber that table 1 polyacrylonitrile fibre makes through pre-oxidation and hydrolysis process and the comparison of natural muscle aspect of performance
In recent years, because more most of synthetic materials have excellent biocompatibility and degradability, biomaterial received increasing concern.Because the high-molecular gel great majority are that block size is bigger at present, and poor mechanical property, response speed are slow, biocompatibility is poor, limit it and restore application in engineering in tissue, especially restore muscle, this just more needs substitute to have reversible fast and accurately features of response.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of a kind of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre comprises the following steps:
(1) preparation of spinning solution:
With mass ratio is 3～12: 3～12: 40 polyacrylonitrile powder, soybean protein powder and water mix, 25 ℃～40 ℃ constant temperature 2 hours, adding concentration is the sodium hydroxide solution of 0.06g/mL～0.08g/mL, the pH value of regulation system is 12, under agitation, with the temperature of whole system by progressively being raised to 70 ℃ in 10 minutes mode of 1 ℃/minute, every liter 10 ℃ constant temperature, constant temperature 2～4 hours; Add the sodium hydroxide solution that concentration is 0.24g/mL～0.96g/mL again, the mass ratio of its addition and the initial polyacrylonitrile of system is 3: 5, regulation system temperature to 90 ℃ constant temperature 1～3 hour;
(2) preparation of coagulating bath:
At 25 ℃ of preparation saturated aqueous sodium sulfates, be 30% glutaraldehyde water solution by 1: 100 volume ratio adding concentration, add the concentrated sulfuric acid then, make that sulfuric acid content is 1～2mol/L in the coagulating bath;
(3) spinning technique of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre:
Spinning solution spinning technique in 20 ℃～25 ℃ coagulating bath with preparation, and carried out crosslinked in 10～15 hours the constant temperature placement in coagulating bath of gained strand, then strand is stretched in air, drying makes hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre at last.
As optimized technical scheme: the aerial draw ratio of back strand that is shaped is 3～5;
Described polyacrylonitrile molecular weight is 50000～70000, and the soybean protein molecular weight is 300000～500000.
The invention has the beneficial effects as follows: prepared intelligent gel fiber is except that having certain biocompatibility, also has faster response speed of pH (the elongation response time is about 1.4s, and the systole response time is about 0.7s), in addition, its degree of shrinkage is 30%～50%, and convergent force is about 8kg/cm
2, all near the corresponding numerical value of human skeletal muscle.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
With always solid be that 60000 polyacrylonitrile powder and molecular weight are that 400000 soybean protein powder mixes in 80ml water by 4: 6 mass ratioes heavily for the molecular weight of 30g, whole system was 30 ℃ of constant temperature 2 hours, add the sodium hydroxide solution that concentration is 0.07g/mL afterwards, the pH value of regulation system is 12, then under agitation with the temperature of whole system with 1 ℃/minute, 10 minutes mode of 10 ℃ every liter constant temperature progressively is raised to 70 ℃ from 30 ℃, constant temperature is 3 hours after reaching 70 ℃, add the sodium hydroxide solution that concentration is 0.6g/mL then, the mass ratio of its addition and the initial polyacrylonitrile of system is 3: 5, regulation system temperature to 90 ℃, constant temperature is 1 hour afterwards.At 25 ℃ of preparation saturated aqueous sodium sulfates, adding concentration by 1: 100 volume ratio is 30% glutaraldehyde water solution, add the concentrated sulfuric acid then, make that sulfuric acid content is 1.5mol/L in the coagulating bath, with spinning solution spinning technique in coagulating bath of preparation, and with the gained strand 22 ℃ in this coagulating bath constant temperature placed 13 hours, afterwards strand is stretched in air 4 times, drying makes hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre that diameter is about 60 μ m, and sample number into spectrum is 2.
Embodiment 2
With always solid be that 50000 polyacrylonitrile powder and molecular weight are that 300000 soybean protein powder mixes in 80ml water by 1: 4 mass ratio heavily for the molecular weight of 30g, whole system was 25 ℃ of constant temperature 2 hours, add the sodium hydroxide solution that concentration is 0.06g/mL afterwards, the pH value of regulation system is 12, then under agitation with the temperature of whole system with 1 ℃/minute, 10 minutes mode of 10 ℃ every liter constant temperature progressively is raised to 70 ℃, constant temperature is 2 hours after reaching 70 ℃, add the sodium hydroxide solution that concentration is 0.24g/mL then, the mass ratio of its addition and the initial polyacrylonitrile of system is 3: 5, regulation system temperature to 90 ℃, constant temperature is 2 hours afterwards.At 25 ℃ of preparation saturated aqueous sodium sulfates, adding concentration by 1: 100 volume ratio is 30% glutaraldehyde water solution, add the concentrated sulfuric acid then, make that sulfuric acid content is 1mol/L in the coagulating bath, with spinning solution spinning technique in coagulating bath of preparation, and with the gained strand 20 ℃ in this coagulating bath constant temperature placed 10 hours, afterwards strand is stretched in air 3 times, drying makes hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre that diameter is about 60 μ m, and sample number into spectrum is 3.
Embodiment 3
With always solid be that 70000 polyacrylonitrile powder and molecular weight are that 500000 soybean protein powder mixes in 80ml water by 4: 1 mass ratioes heavily for the molecular weight of 30g, whole system was 40 ℃ of constant temperature 2 hours, add the sodium hydroxide solution that concentration is 0.08g/mL afterwards, the pH value of regulation system is 12, then under agitation with the temperature of whole system with 1 ℃/minute, 10 minutes mode of 10 ℃ every liter constant temperature progressively is raised to 70 ℃, constant temperature is 4 hours after reaching 70 ℃, add the sodium hydroxide solution that concentration is 0.96g/mL then, the mass ratio of its addition and the initial polyacrylonitrile of system is 3: 5, regulation system temperature to 90 ℃, constant temperature is 3 hours afterwards.At 25 ℃ of preparation saturated aqueous sodium sulfates, adding concentration by 1: 100 volume ratio is 30% glutaraldehyde water solution, add the concentrated sulfuric acid then, make that sulfuric acid content is 2mol/L in the coagulating bath, with spinning solution spinning technique in coagulating bath of preparation, and with the gained strand 22 ℃ in this coagulating bath constant temperature placed 15 hours, afterwards strand is stretched in air 5 times, drying makes hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre that diameter is about 60 μ m, and sample number into spectrum is 4.
Embodiment 4
With always solid be that 70000 polyacrylonitrile powder and molecular weight are that 500000 soybean protein powder mixes in 80ml water by 7: 3 mass ratioes heavily for the molecular weight of 30g, whole system was 30 ℃ of constant temperature 2 hours, add the sodium hydroxide solution that concentration is 0.06g/mL afterwards, the pH value of regulation system is 12, then under agitation with the temperature of whole system with 1 ℃/minute, 10 minutes mode of 10 ℃ every liter constant temperature progressively is raised to 70 ℃ from 30 ℃, constant temperature is 2 hours after reaching 70 ℃, add the sodium hydroxide solution that concentration is 0.96g/mL then, regulation system temperature to 90 ℃, constant temperature is 1 hour afterwards.Spinning solution spinning technique in preparation by the coagulating bath of method preparation noted earlier, and with the gained strand 25 ℃ in this coagulating bath constant temperature placed 12 hours, afterwards strand is stretched in air 5 times, dry, make hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre that diameter is about 60 μ m, sample number into spectrum is 5.
Embodiment 5
With always solid be that 50000 polyacrylonitrile powder and molecular weight are that 300000 soybean protein powder mixes in 80ml water by 4: 6 mass ratioes heavily for the molecular weight of 30g, whole system was 30 ℃ of constant temperature 2 hours, add the sodium hydroxide solution that concentration is 0.08g/mL afterwards, the pH value of regulation system is 12, then under agitation with the temperature of whole system with 1 ℃/minute, 10 minutes mode of 10 ℃ every liter constant temperature progressively is raised to 70 ℃ from 30 ℃, constant temperature is 2 hours after reaching 70 ℃, add the sodium hydroxide solution that concentration is 0.24g/mL then, regulation system temperature to 90 ℃, constant temperature is 1 hour afterwards.Spinning solution spinning technique in preparation by the coagulating bath of method preparation noted earlier, and with the gained strand 25 ℃ in this coagulating bath constant temperature placed 14 hours, afterwards strand is stretched in air 3 times, dry, make diameter and be about 180 μ m hydrolyzed polyacrylonitriles/soybean protein composite intelligent gelatinous fibre, sample number into spectrum is 6.
As a comparison, numbering 1 sample is that pure water is separated the gelatinous fibre sample that polyacrylonitrile makes, during the test result of the relevant performance of each sample is listed in the table below.To be the environment temperature time test fiber that is 25 ℃ elongation takes place the method for testing of its response and transfers the dynamic process that acid condition shrinks to by alkali condition being transferred to alkali condition (0.1mol/L sodium hydroxide solution) by acid condition (0.1mol/L hydrochloric acid solution).
| Sample number into spectrum | Intelligent gel is fibrous | The elongation response time (s) | The systole response time (s) | Convergent force (kg/cm 2) | Degree of shrinkage (%) | Fibre diameter (μ m) |
| 1 | Pure water is separated the polyacrylonitrile gelatinous fibre | ～10 | ～10 | ～9 | 50 | ～60 |
| 2 | Polyacrylonitrile accounts for 40% in the initial powder mixture | 3.63 | 4.32 | ～8 | 44.7 | ～60 |
| 3 | Polyacrylonitrile accounts for 20% in the initial powder mixture | 3.01 | 3.10 | ～7 | 46.2 | ～60 |
| 4 | Polyacrylonitrile accounts for 80% in the initial powder mixture | 2.47 | 2.05 | ～8 | 44.6 | ～60 |
| 5 | Polyacrylonitrile accounts for 70% in the initial powder mixture | 1.35 | 0.63 | ～10 | 33.3 | ～60 |
| 6 | Polyacrylonitrile accounts for 40% in the initial powder mixture | 9.3 | 1.6 | ～10 | 29.8 | ～180 |
Claims (3)
1. the preparation method of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre is characterized in that comprising the following steps:
(1) preparation of spinning solution:
With mass ratio is 3～12: 3～12: 40 polyacrylonitrile powder, soybean protein powder and water mix, 25 ℃～40 ℃ constant temperature 2 hours, adding concentration is the sodium hydroxide solution of 0.06g/mL～0.08g/mL, the pH value of regulation system is 12, under agitation, with the temperature of whole system by progressively being raised to 70 ℃ in 10 minutes mode of 1 ℃/minute, every liter 10 ℃ constant temperature, constant temperature 2～4 hours; Add the sodium hydroxide solution that concentration is 0.24g/mL～0.96g/mL again, the mass ratio of its addition and the initial polyacrylonitrile of system is 3: 5, regulation system temperature to 90 ℃ constant temperature 1～3 hour;
(2) preparation of coagulating bath:
At 25 ℃ of preparation saturated aqueous sodium sulfates, be 30% glutaraldehyde water solution by 1: 100 volume ratio adding concentration, add the concentrated sulfuric acid then, make that sulfuric acid content is 1～2mol/L in the coagulating bath;
(3) spinning technique of hydrolyzed polyacrylonitrile/soybean protein intelligent gelatinous fibre:
Spinning solution spinning technique in 20 ℃～25 ℃ coagulating bath with preparation, and carried out crosslinked in 10～15 hours the constant temperature placement in coagulating bath of gained strand, then strand is stretched in air, drying makes hydrolyzed polyacrylonitrile/soybean protein composite intelligent gelatinous fibre at last.
2. preparation method according to claim 1, the aerial draw ratio of back strand that it is characterized in that being shaped is 3～5.
3. preparation method according to claim 1 is characterized in that described polyacrylonitrile molecular weight is 50000～70000, and the soybean protein molecular weight is 300000～500000.
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| CN104178843B (en) * | 2014-07-30 | 2016-07-06 | 广东洪兴实业有限公司 | A kind of phase transformation blended fiber and manufacture method thereof |
| CN106498553A (en) * | 2016-11-01 | 2017-03-15 | 安徽依采妮纤维材料科技有限公司 | A kind of highly-breathable antiultraviolet modified fibre fabric |
| CN108221179B (en) * | 2017-12-29 | 2021-06-15 | 普宁市新栩纺织有限公司 | Preparation method of moisture-absorbing and heat-emitting antibacterial yarn |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473912A (en) * | 1977-11-18 | 1979-06-13 | Furukawa Electric Co Ltd:The | Production of short synthetic fibers |
| JPH10183465A (en) * | 1996-12-18 | 1998-07-14 | Japan Exlan Co Ltd | Treatment of acrylic fiber |
| CN1431343A (en) * | 2003-01-30 | 2003-07-23 | 中国石化上海石油化工股份有限公司 | Composite fiber of plant protein and acrylon and its manufacturing method |
| CN1587451A (en) * | 2004-09-30 | 2005-03-02 | 东华大学 | Stimulating responsiveness porous hollow gel fiber and its producing method |
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2006
- 2006-04-25 CN CNB2006100259990A patent/CN100344808C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473912A (en) * | 1977-11-18 | 1979-06-13 | Furukawa Electric Co Ltd:The | Production of short synthetic fibers |
| JPH10183465A (en) * | 1996-12-18 | 1998-07-14 | Japan Exlan Co Ltd | Treatment of acrylic fiber |
| CN1431343A (en) * | 2003-01-30 | 2003-07-23 | 中国石化上海石油化工股份有限公司 | Composite fiber of plant protein and acrylon and its manufacturing method |
| CN1587451A (en) * | 2004-09-30 | 2005-03-02 | 东华大学 | Stimulating responsiveness porous hollow gel fiber and its producing method |
Non-Patent Citations (2)
| Title |
|---|
| HPAN/SPI水凝胶纤维的pH刺激相应性能 焦明立等，功能高分子学报，第18卷第1期 2005 * |
| 水解聚丙烯腈/大豆分离蛋白凝胶纤维的电刺激性能 焦明立等，材料研究学报，第19卷第6期 2005 * |
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