CN105256544A - High-performance natural silk fiber and preparation method thereof - Google Patents
High-performance natural silk fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance natural silk fiber and a preparation method thereof. High-performance silk fiber is formed by taking cocoon silk, raw silk, twisted silk or silk weaving yarn as raw materials and then performing contracting or stretching. The method specifically comprises the steps that inorganic salt, acid and water are mixed according to a certain ratio to prepare a silk swelling solution; the silk fiber is immersed into the swelling solution, and then stretching or contracting is performed; lastly, rinsing with clear water, neutralizing treating and drying are performed to obtain the high-performance natural silk fiber. The preparation method is simple, effective and short in process, the breaking strength of the silk fiber prepared through the method is comparable with that of spider silk, and therefore the high-performance natural silk fiber is suitable for application of the advanced technical fields of artificial ligaments, ophthalmological sutures, protective garments and the like.
Description
Technical field
The invention belongs to natural macromolecular material field, be specifically related to a kind of high-performance natural silk fiber and preparation method thereof.
Background technology
Silk is matured silkworm silk glands secretion silk liquid concretionary continuous fiber when cocooing, and is one of animal fiber of utilizing the earliest of the mankind.Different according to food, cocoon silk quilt is divided into mulberry silk, tussah silk, wild silk yarn and ricinus silk etc.The strand taken out from single silk cocoon is called silk, and it borrows silk gum to bond coated forming by two filaments.Extracted out by the silk of several silk cocoon, the strand by means of silk gum bonding parcel is referred to as raw silk.Several raw silks through network and, twist with the fingers or become twisted silk or braided suture after the operation processing such as braiding.As a kind of grade textiles raw material, silk product liking deeply by domestic and international consumer.
In recent years, along with development and the interdisciplinary Cross slot interference of polymer science, the application of silk material is just permeated from traditional textile to high-technology field.Wherein, the research of high-performance silk fiber one of focus just.As a kind of structural protein family macromolecule of non-physiologically active, mechanical property and the aggregated structure of silk have substantial connection.Spider silk has mechanical property excellent especially, as high-strength, Gao Mo, high drawing, high work to break, has huge using value and prospect at the high-technology field such as bulletproof jacket, suture, therefore becomes the focus of current material supply section scholar research.It is found that the best fiber of mechanical property is spider silk, and spider silk is also a kind of structural protein family macromolecule of non-physiologically active.But spider meeting cannibalism, can not produce the spider's thread in batches by mass rearing as silkworm.Research is all the time thought, the essential reason that silk mechanical property can not show a candle to spider silk is that primary structure (also known as amino acid composition and the sequence distribution thereof) difference of silk and spider silk is very large.
For this reason, spider produces in the gene insertion silkworm body of the spider's thread by researcher, prepare the silk containing spider silk fibroin, compared with common silk, mechanical property significantly improves, as intensity improves about 20%, percentage elongation improves about 30%, and this high-performance silk fiber has a extensive future in fields such as bulletproof jacket, high-strength superfine ultra-fine suture, artificial ligament, tendons.The primary structure transforming silk is by the object of transgenic technology, although achieve progress in this regard, but still unrealized important breakthrough, cannot industrialization.The paper that Fudan University Shao Zhengzhong teaches and Regius professor Vollrath teaches delivered by " NATURE " magazine published for 2002; they adopt the natural silk [ShaoZ, the etal.Nature2002 that force technique of reeling off raw silk from cocoons to make curley waste go out mechanical property and spider silk to match in excellence or beauty; 418:741.], this research explanation, the difference of silk and spider silk mechanical property is mainly caused by architectural difference more than fibrinous secondary structure or secondary, and this species diversity can behavior be reduced or eliminates by changing that silkworms spin silk, thus the spider silk of acquisition excellent in mechanical performance.But because silkworm larva health is less and soft, head movement is strong, silk is thin and easily broken, the method therefore by changing silkworms spin silk behavior batch production spider silk is infeasible.
The speed difference major effect that cocoon silk quilt reels off raw silk from cocoons to the Molecular orientational structure of fibroin and partially crystallizable structure, thus causes silk mechanical property to change.Natural silk fiber has benefited from the multilevel hierarchy structure of its uniqueness, itself has had very excellent mechanical property, the optimal path that performance boost on this basis will be preparation high-performance fibroin fiber, if recombinate to natural silk structure, and then by drawing and setting technique, silk is transformed, should can obtain the result of reeling off raw silk from cocoons by force equally in theory; But in type natural silk fiber is mainly anti-parallel ss-sheet crystalline texture, and its aggregated structure is highly stable, be difficult to change, therefore prior art cannot carry out physical extension post processing.Natural silk is generally dissolved rear spinning to obtaining the product of superior performance by prior art; But because dissolution solvent and spin solvent are to the irreversible breaking of silk multilevel hierarchy, as molecular weight reduction, fibrillar structure disintegration etc., cause regenerated silk fiber structural instability, poor mechanical property, although regenerated silk fiber mechanical property can be improved by after-drawing, but performance improves limited, lets alone and becomes the fiber that mechanical property is more excellent compared with natural silk fiber.Therefore, find and a kind ofly transform the method that natural silk structure produces high-performance natural silk fiber, in the application of high-tech sector, there is important value and meaning to silk.
Summary of the invention
The object of this invention is to provide a kind of high-performance natural silk fiber and preparation method thereof, this fiber is directly processed by natural silk and obtains, excellent in mechanical performance, can be widely used in civil and military protection field.
The present invention adopts following technical scheme to realize object of the present invention:
A preparation method for high-performance natural silk fiber, comprises the following steps:
(1) prepare silk swelling solution, described silk swelling solution comprises acid and water;
(2) natural silk fiber is put into above-mentioned silk swelling solution to soak 1 second ~ 1 hour; And natural silk fiber is shunk or stretch processing;
(3) the natural silk fiber after process is carried out washing, neutralisation treatment, then through washing, dry; Obtain high-performance natural silk fiber.
In technique scheme, the acid in step (1) is one or more in formic acid, acetic acid, hydrofluoric acid, phosphoric acid, sulfuric acid; The concentration of acid is 10 ~ 99wt%.Preferably, described acid is the one in formic acid, hydrofluoric acid, phosphoric acid, sulfuric acid; The concentration of described acid is 25 ~ 98wt%.
In preferred technical scheme, the silk swelling solution of described step (1) also comprises inorganic salts; Inorganic salt concentration is 0.1 ~ 10wt%.Inorganic salts are one or more in sodium chloride, potassium chloride, lithium bromide, calcium chloride, zinc chloride, magnesium chloride, lithium rhodanate, sodium sulfocyanate, magnesium rhodanate, calcium nitrate, copper nitrate, calcium carbonate, calcium phosphate.Preferably, described silk swelling solution also comprises inorganic salts; Described inorganic salts are the one in lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate; The concentration of described inorganic salts is 0.5 ~ 5wt%.
Silk of the present invention is natural silk, without regeneration process, is selected from one or more in mulberry silk, tussah silk, wild silk yarn, ricinus silk.Natural silk fiber is the compound of one or more in silk, raw silk, twisted silk, weaving thread.
In technique scheme, step (2), shrinkage factor during shrink process is 1 ~ 80%; Draw ratio during stretch processing is 1.1 ~ 5 times.The present invention can stretch or shrink process to it while natural silk fiber soaks, and also can stretch or shrink process to it after natural silk fiber soaks again.
Preferably, shrinkage factor during described shrink process is 20 ~ 70%; Draw ratio during described stretch processing is 1.1 ~ 3.2 times; Soak time is 5 seconds ~ 5 minutes.
The present invention carries out physical extension/contraction modification to natural silk fiber (comprising silk, raw silk, twisted silk, weaving thread etc.), breach the not tensile technical barrier of natural silk fiber, achieve the huge leap forward of natural silk fibrous mechanical property, thus meet the application requirement of silk at special dimension, as bulletproof jacket, artificial ligament, ophthalmic sutures etc.Therefore the invention also discloses the high-performance natural silk fiber prepared according to above-mentioned preparation method.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention achieves the uniaxial direct tensile process of natural silk fiber first, thus reaches the effect improving natural silk mechanical property, and fracture strength reaches more than 1000MPa, elongation at break reaches more than 50%; Overcome the not tensile defect of existing natural silk, achieve beyond thought technique effect.
(2) instant invention overcomes the defect that prior art is mainly carried out transgenosis to silkworm or forced process of reeling off raw silk from cocoons, by comparison, the natural silk fracture strength that the present invention obtains is the highest improves 2 times, reach more than 1GPa, and can be used for producing high-performance raw silk, twisted silk, weaving thread etc., meet and produce upper application.
(3) solvent parameter that method choice of the present invention is suitable and dissolution conditions, silk is made not occur dissolve and remove beta sheet structure, thus regulate and control to provide window for the structure of modification of natural silk fiber and performance, obtain high-performance natural silk fiber by simple method.
(4) processing method of raising natural fiber strength disclosed by the invention is simply efficient, directly can dock with existing product production line, realize the mass production of high-performance natural silk fiber.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of natural silk fiber treatment front and rear surfaces in embodiment one;
Fig. 2 is the scanning electron microscope (SEM) photograph of section before and after natural silk fiber treatment in embodiment one;
Fig. 3 is the infrared spectrum in embodiment two before and after natural silk fiber treatment;
Fig. 4 is the Raman spectrogram in embodiment two before and after natural silk fiber treatment.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment one
(1) preparing natural silk swelling solution: 98wt% formic acid is diluted with water to 80%, then adds lithium bromide and is made into 80% formic acid solution containing 2% lithium bromide, be silk swelling solution;
(2) Bombyx-mori Bave is immersed in 30s in the swelling solution of step (1), controls silk simultaneously and be contracted to 60% of former length, obtain shrinking silk;
(3) the contraction silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed in 60 DEG C of baking ovens to dry and dryly obtains high-performance natural silk fiber again.
Table 1 is the mechanical stretch data of Bombyx-mori Bave before and after process, and have excellent ductility by the silk after technical scheme process provided by the present invention, elongation at break reaches more than 50%.
The mechanical stretch data of silk before and after table 1 processes
| Sample | Elongation at break (%) | Work to break (MJ/m 3） |
| Former silk | 21.1 | 64.5 |
| Process silk | 52.3 | 72.8 |
Accompanying drawing 1, accompanying drawing 2 and table 1 are ESEM before and after the process of above-mentioned high-performance natural silk fiber and mechanical stretch performance data.As seen from Figure 1, solid arrow is machine direction, and after process, the orderly nanometer fibril orientation texture of silk internal height is destroyed; As seen from Figure 2, the nanofibrillar structures of silk cocoon inside becomes fluffy, high-visible; Illustrate that the present invention effectively removes natural silk beta sheet structure, thus significantly improve natural silk fibre property.In addition, as shown in Table 1, after process, natural mulberry silk extension at break improves significantly to more than 50%, and work to break improves about 10%.
Embodiment two
(1) prepare silk swelling solution: 98% formic acid is diluted with water to 80%, then add calcium chloride and be made into 80% formic acid solution containing 2% calcium chloride, be silk swelling solution;
(2) Bombyx-mori Bave is immersed in 30s in the swelling solution of step (1), then stretching silk is to 2 times of former length, obtains stretching silk;
(3) the stretching silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 60 DEG C of baking ovens and obtains high-performance natural silk fiber again.
Table 2 is the mechanical stretch data of silk before and after process, and have excellent intensity by the silk after technical scheme process provided by the present invention, fracture strength reaches more than 900MPa.
The mechanical stretch data of silk before and after table 2 processes
| Sample | Fracture strength (MPa) |
| Former silk | 450 |
| Stretching silk | 920 |
Accompanying drawing 3, accompanying drawing 4 and table 2 are infrared spectrum, Raman spectrogram and mechanical property before and after the process of above-mentioned high-performance natural silk fiber.As seen from Figure 3, after process, the degree of crystallinity of silk inside is damaged, obvious reduction compared with before process; As seen from Figure 4, after process stretches, the degree of molecular orientation of silk fiber significantly improves; Be conducive to the raising of natural silk mechanical property.In addition, as shown in Table 2, after stretch processing, the fracture strength of silk significantly improves, and fracture strength reaches more than 800MPa.
Embodiment three
(1) silk swelling solution is prepared: in 98% formic acid, add lithium rhodanate be made into formic acid solution containing 1% lithium rhodanate, be silk swelling solution;
(2) 20-22D raw silk is immersed in 50s in the swelling solution of step (1), then controls silk and be contracted to 30% of former length, obtain shrinking raw silk;
(3) the contraction raw silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 70 DEG C of baking ovens and obtains high-performance natural silk fiber again.
Table 3 is the mechanical stretch data of raw silk before and after process, and have excellent ductility by the raw silk after technical scheme process provided by the present invention, elongation at break reaches more than 50%, and work to break improves about 20%.
The mechanical stretch data of raw silk before and after table 3 processes
| Sample | Elongation at break (%) | Work to break (MJ/m 3） |
| Former silk | 21.1 | 354.2 |
| Process silk | 58.5 | 412.8 |
Embodiment four
(1) silk swelling solution is prepared: in 90% trifluoroacetic acid, add magnesium chloride be made into hydrofluoric acid solution containing 1% magnesium chloride, be silk swelling solution;
(2) 20-22D raw silk is immersed in 50s in the swelling solution of step (1), stretching raw silk is to 1.5 times of former length simultaneously, obtains stretching raw silk;
(3) the stretching raw silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 55 DEG C of baking ovens and obtains high-performance natural silk fiber again.
Table 4 is the mechanical stretch data of raw silk before and after process, and have excellent intensity by the raw silk after technical scheme process provided by the present invention, fracture strength is to more than 800MPa.
The mechanical stretch data of raw silk before and after table 4 processes
| Sample | Ultimate strength (cN) |
| Primary silk | 81.2 |
| Stretching raw silk | 105.6 |
Embodiment five
(1) silk swelling solution is prepared: 98% formic acid is diluted to 90% and is silk swelling solution;
(2) silk braided suture diameter being about 0.22mm is immersed in 20s in the swelling solution of step (1), and stretching braided suture simultaneously, to 1.3 times of former length, obtains stretching braided suture;
(3) the stretching braided suture that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 60 DEG C of baking ovens and obtains high-performance natural silk fiber again.
Table 5 is the mechanical stretch data of silk braided suture before and after process, significantly improves, reach more than 3000cN by the stretching braided suture ultimate strength after technical scheme process provided by the present invention.
The mechanical stretch data of silk braided suture before and after table 5 processes
| Sample | Ultimate strength (cN) |
| Former weaving thread (4#) | 2787.8 |
| Stretching weaving thread | 3875.6 |
Embodiment six
(1) silk swelling solution is prepared: diluting concentrated sulfuric acid to 30% is silk swelling solution;
(2) tussah silk is immersed in 50s in the swelling solution of step (1), is then stretched to 3 times of former length, then obtains stretching tussah silk;
(3) the stretching tussah silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 60 DEG C of baking ovens and obtains high-performance natural silk fiber again;
Table 6 is the mechanical stretch data of tussah silk before and after process, significantly improves, reach more than 1000MPa by the stretching tussah silk ultimate strength after technical scheme process provided by the present invention.
The mechanical stretch data of tussah silk before and after table 6 processes
| Sample | Fracture strength (MPa) |
| Former tussah silk | 430 |
| Stretching tussah silk | 1100 |
Embodiment seven
(1) silk swelling solution is prepared: SPA is diluted to 25% and is silk swelling solution;
(2) ricinus silk is immersed in 30s in the swelling solution of step (1), is then stretched to 2 times of former length, obtains stretching ricinus silk;
(3) the stretching tussah silk that obtains of step (2) is after deionized water washing, and then in 1wt% sodium hydrate aqueous solution and unnecessary acid, washing is placed on drying in 60 DEG C of baking ovens and obtains high-performance natural silk fiber again.
Table 7 is the mechanical stretch data of ricinus silk before and after process, significantly improves, reach more than 780MPa by the stretching tussah silk ultimate strength after technical scheme process provided by the present invention.
The mechanical stretch data of ricinus silk before and after table 7 processes
| Sample | Fracture strength (MPa) |
| Former castor-oil plant silk | 463 |
| Stretching castor-oil plant silk | 783 |
The concentration of the present embodiment is all mass concentration.The postprocessing working procedures of the present invention to existing natural silk fibre (comprising silk, raw silk, twisted silk, weaving thread etc.) can be transformed its mechanical property, thus constructs the natural silk fiber with high-performance, high drawing.
Claims (10)
1. a preparation method for high-performance natural silk fiber, is characterized in that, comprises the following steps:
(1) prepare silk swelling solution, described silk swelling solution comprises acid and water;
(2) natural silk fiber is put into above-mentioned silk swelling solution to soak 1 second ~ 1 hour; And natural silk fiber is shunk or stretch processing;
(3) the natural silk fiber after process is carried out washing, neutralisation treatment, then through washing, dry; Obtain high-performance natural silk fiber.
2. the preparation method of high-performance natural silk fiber according to claim 1, it is characterized in that: in step (1), described acid is one or more in formic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, phosphoric acid, sulfuric acid; The concentration of described acid is 10 ~ 99wt%.
3. the preparation method of high-performance natural silk fiber according to claim 2, it is characterized in that: in step (1), described acid is the one in formic acid, hydrofluoric acid, phosphoric acid, sulfuric acid; The concentration of described acid is 25 ~ 98wt%.
4. the preparation method of high-performance natural silk fiber according to claim 1, it is characterized in that: in step (1), described silk swelling solution also comprises inorganic salts; Described inorganic salts are one or more in sodium chloride, potassium chloride, lithium bromide, calcium chloride, zinc chloride, magnesium chloride, lithium rhodanate, sodium sulfocyanate, magnesium rhodanate, calcium nitrate, copper nitrate, calcium carbonate, calcium phosphate; The concentration of described inorganic salts is 0.1 ~ 10wt%.
5. the preparation method of high-performance natural silk fiber according to claim 4, it is characterized in that: in step (1), described silk swelling solution also comprises inorganic salts; Described inorganic salts are the one in lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate; The concentration of described inorganic salts is 0.5 ~ 5wt%.
6. the preparation method of high-performance natural silk fiber according to claim 1, it is characterized in that: in step (2), described natural silk is one or more in mulberry silk, tussah silk, wild silk yarn, ricinus silk.
7. the preparation method of high-performance natural silk fiber according to claim 1, it is characterized in that: in step (2), described natural silk fiber is the compound of one or more in silk, raw silk, twisted silk, weaving thread.
8. the preparation method of high-performance natural silk fiber according to claim 1, it is characterized in that: in step (2), shrinkage factor during described shrink process is 1 ~ 80%; Draw ratio during described stretch processing is 1.1 ~ 5 times.
9. the preparation method of high-performance natural silk fiber according to claim 8, it is characterized in that: in step (2), shrinkage factor during described shrink process is 20 ~ 70%; Draw ratio during described stretch processing is 1.1 ~ 3.2 times; Soak time is 5 seconds ~ 5 minutes.
10. the high-performance natural silk fiber for preparing of the preparation method of any one high-performance natural silk fiber according to claims 1 to 9.
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Address after: 226300 New Century Avenue, Tongzhou District, Nantong, Jiangsu 266 Patentee after: NANTONG TEXTILE & SILK INDUSTRIAL TECHNOLOGY Research Institute Address before: Jiangsu province Nantong City Road 226018, No. 58, Nantong Industrial Technology Research Institute No. 1 building 7 floor Patentee before: NANTONG TEXTILE & SILK INDUSTRIAL TECHNOLOGY Research Institute |
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Effective date of registration: 20230614 Address after: No. 8, Beibang East, Maming Village, Zhouquan Town, Tongxiang, Jiaxing, Zhejiang Province 314513 Patentee after: Zhejiang Bensi Technology Co.,Ltd. Address before: 226300 no.266, New Century Avenue, Tongzhou District, Nantong City, Jiangsu Province Patentee before: NANTONG TEXTILE & SILK INDUSTRIAL TECHNOLOGY Research Institute |