WO2017070873A1 - 一种高性能天然蚕丝纤维及其制备方法 - Google Patents

一种高性能天然蚕丝纤维及其制备方法 Download PDF

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Publication number
WO2017070873A1
WO2017070873A1 PCT/CN2015/093139 CN2015093139W WO2017070873A1 WO 2017070873 A1 WO2017070873 A1 WO 2017070873A1 CN 2015093139 W CN2015093139 W CN 2015093139W WO 2017070873 A1 WO2017070873 A1 WO 2017070873A1
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Prior art keywords
silk
silk fiber
acid
natural silk
performance
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PCT/CN2015/093139
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English (en)
French (fr)
Inventor
张锋
左保齐
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南通纺织丝绸产业技术研究院
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Priority to EP15906939.2A priority Critical patent/EP3369859B1/en
Priority to PCT/CN2015/093139 priority patent/WO2017070873A1/zh
Publication of WO2017070873A1 publication Critical patent/WO2017070873A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/67—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk

Definitions

  • the invention belongs to the field of natural polymer materials, and particularly relates to a high performance natural silk fiber and a preparation method thereof.
  • Silk is a continuous filament obtained by solidification of the silk gland secretion silky silk crust, which is one of the earliest animal fibers used by humans. Silk is divided into mulberry silk, tussah silk, celestial silk and ramie silk according to different foods.
  • the thread drawn from a single silkworm cocoon is called silk, which is made by bonding two single fibers with silk glue.
  • the silkworms of several silkworm cocoons are extracted, and the silk yarns wrapped by silk glue are called raw silk.
  • a few raw silks are processed into a twisted wire or a braided suture after being processed by a process such as twisting, twisting, or weaving.
  • As a high-grade textile raw material silk products are deeply loved by consumers at home and abroad.
  • spiders can be similarly disabled, and they cannot be mass-produced in large quantities like silkworms. It has been believed that the mechanical properties of silk are far less than the essential reason for spider silk.
  • the primary structure of silk and spider silk also known as amino acid composition and its sequence distribution
  • the mechanical properties are significantly improved, such as an increase in strength of about 20%, elongation. Increased by about 30%, the high-performance silk fiber has broad application prospects in the fields of bulletproof vests, high-strength ultra-fine sutures, artificial ligaments, and tendons.
  • the purpose of transgenic technology is to transform the primary structure of silk. Although progress has been made in this respect, no major breakthrough has been achieved and it is impossible to industrialize.
  • Natural silk fiber benefits from its unique multi-stage structure and has excellent mechanical properties.
  • the performance improvement based on this will be the best way to prepare high-performance silk protein fiber, such as natural silk structure. Recombination, and then transforming the silk by the stretching and setting process, theoretically, the result of strong spinning can be obtained as well; however, the formed natural silk fiber is mainly an anti-parallel ⁇ -folded crystal structure, and its aggregate structure is very stable. It is difficult to change, so the prior art cannot perform physical stretching treatment.
  • natural silk is generally dissolved and spun to obtain a product with higher performance; however, due to the irreversible damage of the multi-stage structure of the silk by the dissolution solvent and the spinning solvent, such as a decrease in molecular weight and disintegration of the fibril structure, the regenerated silk is caused.
  • the fiber structure is unstable and the mechanical properties are poor.
  • the mechanical properties of the regenerated silk fiber can be improved by post-stretching, the performance improvement is limited, not to mention the fiber which is superior in mechanical properties compared with the natural silk fiber. Therefore, looking for a method for transforming natural silk structure to obtain high-performance natural silk fiber has important value and significance for the application of silk in high-tech fields.
  • An object of the present invention is to provide a high-performance natural silk fiber and a preparation method thereof, which are directly processed by natural silk, have excellent mechanical properties, and can be widely used in the fields of civil and military protection.
  • a method for preparing a high performance natural silk fiber comprising the steps of:
  • the treated natural silk fiber is washed with water, neutralized, washed with water, and dried to obtain a high-performance natural silk fiber.
  • the acid in the step (1) is one or more of formic acid, acetic acid, hydrofluoric acid, phosphoric acid, and sulfuric acid; and the concentration of the acid is 10 to 99% by weight.
  • the acid is one of formic acid, hydrofluoric acid, phosphoric acid, and sulfuric acid; and the concentration of the acid is 25 to 98% by weight.
  • the concentration of the inorganic salt is 0. l ⁇ 10wt%.
  • the inorganic salts are sodium chloride, potassium chloride, lithium bromide, calcium chloride, zinc chloride, magnesium chloride, lithium thiocyanate, sodium thiocyanate, magnesium thiocyanate, calcium nitrate, copper nitrate, calcium carbonate, calcium phosphate.
  • the concentration of the inorganic salt is 0. 5 ⁇ 5wt%.
  • the concentration of the inorganic salt is 0. 5 ⁇ 5wt%.
  • the silk of the present invention is a natural silk, which is selected from one or more of mulberry silk, tussah silk, celestial silk, and ramie silk without regeneration treatment.
  • the natural silk fiber is a composite of one or more of a silk, a raw silk, a twisted wire, and a braided wire.
  • the shrinkage ratio during the shrinkage treatment is 1 to 80%; and the draw ratio at the time of the stretching treatment is 1. 1 to 5 times.
  • the present invention can be stretched or shrunk while the natural silk fiber is immersed, or it can be stretched or shrunk after being immersed in the natural silk fiber.
  • the shrinkage ratio in the shrinking treatment is 20 to 70%; the stretching ratio in the stretching treatment is 1. 1 to 3. 2 times; the soaking time is 5 seconds to 5 minutes.
  • the present invention physically stretches/shrinks and modifies natural silk fibers (including silk, raw silk, crepe, braided threads, etc.), breaks through the technical problem that natural silk fibers cannot be stretched, and realizes natural silk fibers.
  • natural silk fibers including silk, raw silk, crepe, braided threads, etc.
  • the present invention has the following advantages over the prior art: [0019] (1) The invention realizes the direct stretching treatment of the natural silk fiber for the first time, thereby achieving the effect of improving the mechanical properties of the natural silk, the breaking strength reaches more than 1000 MPa, and the elongation at break reaches 50% or more; Natural silk can not be stretched, and unexpected technical effects have been achieved.
  • the present invention overcomes the defects of the prior art mainly for transgenic or forced spinning treatment of silkworms, and the natural silk obtained by the invention has a breaking strength up to 2 times, up to l"lGPa Above, and can be used to produce high-performance raw silk, twisted wire, braided wire, etc., in line with production applications.
  • the method of the invention selects suitable solvent parameters and dissolution conditions, so that the silk does not dissolve and removes the ⁇ _fold structure, thereby providing a window for structural transformation and performance regulation of the natural silk fiber, obtained by a simple method. High performance natural silk fiber.
  • the processing method for improving the strength of natural fibers disclosed in the present invention is simple and efficient, and can be directly connected with the existing product production line to realize mass production of high-performance natural silk fibers.
  • 1 is a scanning electron micrograph of the surface of the natural silk fiber before and after treatment in the first embodiment
  • FIG. 2 is a scanning electron micrograph of a section of a natural silk fiber before and after treatment in the first embodiment
  • Example 4 is a Raman spectrum before and after treatment of natural silk fibers in Example 2.
  • Figure 1, Figure 2 and Table 1 show the scanning electron microscopy and mechanical tensile performance data of the above-mentioned high performance natural silk fiber before and after treatment. It can be seen from Fig. 1 that the solid arrow is the fiber direction. After treatment, the highly ordered nanofibril orientation structure inside the silk is destroyed; as can be seen from Fig. 2, the nanofibrillar structure inside the silkworm cocoon becomes fluffy and clearly visible; The invention effectively removes the ⁇ -fold structure of the natural silk, thereby greatly improving the performance of the natural silk fiber. In addition, as shown in Table 1, after treatment, the natural mulberry silk elongation at break was significantly increased to over 50%, and the work of fracture was increased by about 10%.
  • Step (2) obtained by drawing the twisted silk wire after washing with deionized water, then adding excess acid in an aqueous solution of sodium hydroxide, washing again, and drying in an oven at 60 ° C to obtain a high performance natural.
  • Silk fiber obtained by drawing the twisted silk wire after washing with deionized water, then adding excess acid in an aqueous solution of sodium hydroxide, washing again, and drying in an oven at 60 ° C to obtain a high performance natural.
  • Silk fiber obtained by drawing the twisted silk wire after washing with deionized water, then adding excess acid in an aqueous solution of sodium hydroxide, washing again, and drying in an oven at 60 ° C to obtain a high performance natural.
  • Table 2 shows the mechanical tensile data of the crepe before and after the treatment.
  • the crepe treated according to the technical solution provided by the present invention has excellent strength and the breaking strength reaches 900 MPa or more.
  • FIG. 3 Sample Breaking Strength (MPa) Original Filament 450 Stretched Filament 920
  • FIG. 4 and Table 2 are infrared spectra, Raman spectra and mechanical properties of the above-mentioned high performance natural silk fibers before and after treatment. It can be seen from Fig. 3 that after treatment, the crystallinity inside the silk is destroyed, which is significantly reduced compared with that before treatment. It can be seen from Fig. 4 that the molecular orientation of the silk fiber is significantly improved after the treatment is stretched; it is beneficial to the mechanical properties of the natural silk. Improvement. Further, as is clear from Table 2, after the stretching treatment, the breaking strength of the silk was remarkably improved, and the breaking strength was at least SOOMPa.
  • Table 3 shows the mechanical tensile data of the raw silk before and after the treatment.
  • the raw silk treated according to the technical solution provided by the present invention has excellent ductility, the elongation at break is more than 50%, and the work of fracture is increased by about 20%.
  • Table 4 is the mechanical tensile data of the raw silk before and after the treatment, the raw materials processed according to the technical solution provided by the present invention Table 4 Mechanical tensile data of raw silk before and after treatment
  • Step (2) The obtained stretched braided suture is washed with deionized water, then with excess acid in a 1 wt% aqueous sodium hydroxide solution, washed again, and dried in an oven at 60 ° C to obtain High performance natural silk fiber.
  • Table 5 shows the mechanical tensile data of the silk-knitted suture before and after the treatment. According to the technical solution provided by the present invention, the tensile strength of the stretched braided suture after treatment is significantly improved, reaching 3000 cN or more.
  • Step (2) The obtained tussah silk is washed with deionized water, then with excess acid in a 1 wt% aqueous sodium hydroxide solution, washed again, and placed in an oven at 60 ° C to dry.
  • Performance natural silk fiber [0064] Table 6 shows the mechanical tensile data of the tussah silk before and after the treatment, and the tensile strength of the stretched tussah silk treated according to the technical solution provided by the present invention is remarkably improved to reach 1000 MPa or more.
  • Step (2) The obtained tussah silk is washed with deionized water, then with excess acid in a 1 wt% aqueous sodium hydroxide solution, washed again, and placed in an oven at 60 ° C to dry.
  • Table 7 shows the mechanical tensile data of the ramie silk before and after the treatment, and the tensile strength of the stretched tussah silk treated according to the technical solution provided by the present invention is remarkably improved to reach 780 MPa or more.
  • the concentrations of this embodiment are all mass concentrations.
  • the invention can modify the mechanical properties of the existing natural silk fiber products (including silk, raw silk, twisted wire, braided wire, etc.) to construct a natural silk fiber with high performance and high elongation. .

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Husbandry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

一种高性能天然蚕丝纤维及其制备方法。以茧丝、生丝、捻线丝或蚕丝编织线为原料，经过收缩或者拉伸后成为高性能蚕丝纤维；具体为无机盐、酸和水按一定比例混合制成蚕丝溶胀液；将蚕丝纤维浸入溶胀液中，并实施拉伸/收缩；最后进行清水漂洗、中和处理、烘干得到高性能蚕丝纤维。该制备方法简单有效、流程短，由该方法制得的蚕丝纤维断裂强度与蜘蛛丝相媲美，因此适合于高新技术领域的应用，如人工韧带、眼科缝线、防护服等。

Description

发明名称： 一种高性能天然蚕丝纤维及其制备方法 技术领域
[0001] 本发明属于天然高分子材料领域， 具体涉及一种高性能天然蚕丝纤维及其制备 方法。
背景技术
[0002] 蚕丝是熟蚕结茧时绢丝腺分泌丝液凝固而成的连续长纤维， 是人类最早利用的 动物纤维之一。 根据食物不同， 蚕丝被分为桑蚕丝、 柞蚕丝、 天蚕丝和蓖麻蚕 丝等。 从单个蚕茧抽得的丝条称为茧丝， 它由两根单纤维借丝胶粘合包覆而成 。 将几个蚕茧的茧丝抽出， 借丝胶粘合包裹而成的丝条称之为生丝。 几根生丝 经过络、 并、 捻或编织等工序加工后成为捻线丝或编织缝合线。 作为一种高档 纺织品原料， 蚕丝制品深受国内外消费者的喜爱。
[0003] 近年来， 随着高分子科学的发展及学科间的交叉渗透， 蚕丝材料的应用正从传 统纺织品向高新技术领域渗透。 其中， 高性能蚕丝纤维的研究正是热点之一。 作为一种非生理活性的结构蛋白质类高分子， 蚕丝的力学性能与聚集态结构有 密切关系。 蜘蛛丝具有特别优异的力学性能， 如高强、 高模、 高伸长、 高断裂 功， 在防弹衣、 缝合线等高新技术领域有巨大的应用价值与前景， 因此成为当 今材料科学家研究的热点。 人们发现力学性能最好的纤维是蜘蛛丝， 而蜘蛛丝 也是一种非生理活性的结构蛋白质类高分子。 然而， 蜘蛛会同类相残， 不能像 蚕一样通过大量饲养批量生产蛛丝。 一直以来的研究认为， 蚕丝力学性能远不 如蜘蛛丝的本质原因在于蚕丝和蜘蛛丝的一级结构 （又称氨基酸组成及其序列 分布） 差别很大。
[0004] 为此， 研究人员将蜘蛛产生蛛丝的基因植入蚕体内， 制备出含蜘蛛丝蛋白的蚕 丝， 与普通蚕丝相比， 力学性能显著提高， 如强度提高约 20%， 伸长率提高约 30 %， 该高性能蚕丝纤维在防弹衣、 高强超细缝合线、 人工韧带、 肌腱等领域应用 前景广阔。 通过转基因技术的目的在于改造蚕丝的一级结构， 尽管在此方面取 得了进展， 但仍未实现重大突破， 无法工业化。 2002年出版的 《NATURE》 杂志 发表了复旦大学邵正中教授和英国牛津大学 Vol lrath教授的论文， 他们采用强 迫抽丝工艺使蚕吐出力学性能与蜘蛛丝媲美的天然蚕丝 [Shao Z, et al.
Nature 2002； 418： 741. ] , 该研究说明， 蚕丝和蜘蛛丝力学性能的差异主要是由 纤维蛋白的二级结构或二级以上的结构差异造成的， 这种差异可以通过改变蚕 吐丝行为来缩小或消除， 从而获得力学性能优异的蜘蛛蚕丝。 但是由于家蚕幼 虫身体较小而软、 头部活动性强、 蚕丝细而易断， 因此通过改变蚕吐丝行为批 量生产蜘蛛丝的方法不可行。
[0005] 蚕丝被抽丝的速度差异主要影响到蚕丝蛋白的分子取向结构与部分结晶结构， 从而引起蚕丝力学性能变化。 天然蚕丝纤维得益于其独特的多级结构构造， 本 身已具有非常优异的力学性能， 在此基础上的性能提升将是制备高性能蚕丝蛋 白纤维的最佳途径， 如能对天然蚕丝结构进行重组， 进而通过拉伸定型工艺对 蚕丝进行改造， 理论上应同样可以获得强抽丝的结果； 然而， 已成型的天然蚕 丝纤维主要为反平行 β -折叠结晶结构， 其聚集态结构非常稳定， 难以改变， 因 此现有技术无法进行物理拉伸后处理。 现有技术一般将天然蚕丝溶解后纺丝以 期获得较高性能的产品； 但是由于溶解溶剂与纺丝溶剂对蚕丝多级结构的不可 逆破坏， 如分子量降低、 原纤结构崩解等， 导致再生蚕丝纤维结构不稳定、 力 学性能差， 尽管通过后拉伸可以提高再生蚕丝纤维力学性能， 但性能提高有限 ， 更不要说成为与天然蚕丝纤维相比力学性能更优异的纤维。 因此， 寻找一种 改造天然蚕丝结构制取高性能天然蚕丝纤维的方法， 对蚕丝在高技术领域的应 用具有重要价值与意义。
发明概述
问题的解决方案
技术解决方案
[0006] 本发明的目的是提供一种高性能天然蚕丝纤维及其制备方法， 该纤维由天然蚕 丝直接处理得到， 力学性能优异， 可广泛用于民用和军用防护领域。
[0007] 本发明采用如下技术方案实现本发明的目的：
[0008] 一种高性能天然蚕丝纤维的制备方法， 包括以下步骤：
[0009] ( 1 ) 制备蚕丝溶胀液， 所述蚕丝溶胀液包括酸与水； [0010] ( 2 ) 将天然蚕丝纤维放入上述蚕丝溶胀液中浸泡 1秒〜 1小时； 并对天然蚕丝 纤维进行收缩或者拉伸处理；
[0011] ( 3 ) 将处理后的天然蚕丝纤维进行水洗、 中和处理， 再经水洗、 烘干； 得到 高性能天然蚕丝纤维。
[0012] 上述技术方案中， 步骤 （1 ) 中的酸为甲酸、 乙酸、 氢氟酸、 磷酸、 硫酸中的 一种或几种； 酸的浓度为 10〜99wt%。 优选的， 所述酸为甲酸、 氢氟酸、 磷酸、 硫酸中的一种； 所述酸的浓度为 25〜98wt%。
[0013] 优选的技术方案中， 所述步骤 （1 ) 的蚕丝溶胀液还包括无机盐； 无机盐浓度 为 0. l〜10wt%。 无机盐为氯化钠、 氯化钾、 溴化锂、 氯化钙、 氯化锌、 氯化镁 、 硫氰酸锂、 硫氰酸钠、 硫氰酸镁、 硝酸钙、 硝酸铜、 碳酸钙、 磷酸钙中的一 种或几种。 优选的， 所述蚕丝溶胀液还包括无机盐； 所述无机盐为溴化锂、 氯 化钙、 氯化镁、 硫氰酸锂中的一种； 所述无机盐的浓度为 0. 5〜5wt%。
[0014] 本发明的蚕丝为天然蚕丝， 未经再生处理， 选自桑蚕丝、 柞蚕丝、 天蚕丝、 蓖 麻蚕丝中的一种或几种。 天然蚕丝纤维为茧丝、 生丝、 捻线丝、 编织线中的一 种或几种的复合物。
[0015] 上述技术方案中， 步骤 （2 ) ， 收缩处理时的收缩率为 1〜80%； 拉伸处理时的 拉伸倍数为 1. 1〜5倍。 本发明可以在天然蚕丝纤维浸泡的同时对其进行拉伸或 者收缩处理， 也可以在天然蚕丝纤维浸泡后再对其进行拉伸或者收缩处理。
[0016] 优选的， 所述收缩处理时的收缩率为 20〜70%； 所述拉伸处理时的拉伸倍数为 1 . 1〜3. 2倍； 浸泡时间为 5秒〜 5分钟。
[0017] 本发明对天然蚕丝纤维 （包括茧丝、 生丝、 捻线丝、 编织线等） 进行物理拉伸 /收缩改性， 突破了天然蚕丝纤维不能拉伸的技术难题， 实现了天然蚕丝纤维力 学性能的巨大飞跃， 从而满足蚕丝在特殊领域的应用要求， 如防弹衣、 人工韧 带、 眼科缝线等。 因此本发明还公开了根据上述制备方法制备得到的高性能天 然蚕丝纤维。
发明的有益效果
有益效果
[0018] 由于上述技术方案运用， 本发明与现有技术相比具有下列优点： [0019] (1)本发明首次实现了天然蚕丝纤维的直接拉伸处理， 从而达到了提高天然蚕 丝力学性能的效果， 断裂强度达到 lOOOMPa以上、 断裂伸长率达到 50%以上； 克 服了现有天然蚕丝不能拉伸的缺陷， 取得了意想不到的技术效果。
[0020] (2)本发明克服了现有技术主要对蚕进行转基因或强迫抽丝处理的缺陷， 与之 相比， 本发明获得的天然蚕丝断裂强度最高可提高 2倍， 达至 l」lGPa以上， 且可用 于制取高性能生丝、 捻线丝、 编织线等， 符合生产上应用。
[0021] (3) 本发明的方法选择合适的溶剂参数与溶解条件， 使得蚕丝不发生溶解而去 除 β _折叠结构， 从而为天然蚕丝纤维的结构改造与性能调控提供窗口， 通过简 单的方法获得了高性能天然蚕丝纤维。
[0022] 本发明公开的提高天然纤维强度的加工方法简单高效， 可直接与现有产品生产 线对接， 实现高性能天然蚕丝纤维的批量化生产。
对附图的简要说明
附图说明
[0023] 图 1为实施例一中天然蚕丝纤维处理前后表面的扫描电镜图；
[0024] 图 2为实施例一中天然蚕丝纤维处理前后断面的扫描电镜图；
[0025] 图 3为实施例二中天然蚕丝纤维处理前后的红外谱图；
[0026] 图 4为实施例二中天然蚕丝纤维处理前后的拉曼谱图。
发明实施例
本发明的实施方式
[0027] 下面结合附图及实施例对本发明作进一步描述：
[0028] 实施例一
[0029] ( 1 ) 配制天然蚕丝溶胀液： 将 98wt%¥酸用水稀释至 80%， 然后加入溴化锂配 成含 2%溴化锂的 80%甲酸溶液， 即为蚕丝溶胀液；
[0030] ( 2 ) 将桑蚕茧丝浸没于步骤 （1 ) 的溶胀液中 30s， 同时控制茧丝收缩至原长 的 60%， 得到收缩茧丝；
[0031] ( 3 ) 步骤 （2 ) 得到的收缩茧丝在去离子水洗涤后， 然后在 lwt%氢氧化钠水溶 液中和多余的酸， 再次水洗后置于 60°C烘箱中烘干燥得到高性能天然蚕丝纤维 [0032] 表 1为处理前后桑蚕茧丝的力学拉伸数据， 按本发明所提供的技术方案处理后 的茧丝具有优异的延展性， 断裂伸长率达到 50%以上。
[0033] 表 1 处理前后茧丝的力学拉伸数据
[] [表 1]
Figure imgf000006_0001
[0034] 附图 1、 附图 2和表 1为上述高性能天然蚕丝纤维处理前后的扫描电镜和力学拉 伸性能数据。 由图 1可见， 实线箭头为纤维方向， 处理后， 蚕丝内部高度有序的 纳米原纤取向结构遭到破坏； 由图 2可见， 蚕茧内部的纳米原纤结构变得蓬松、 清晰可见； 说明本发明有效去除天然蚕丝 β _折叠结构， 从而大幅提高天然蚕丝 纤维性能。 此外， 由表 1可知， 处理后， 天然桑蚕丝断裂伸长显著提高到 50%以 上， 断裂功提高约 10%。
[0035] 实施例二
[0036] ( 1 ) 配制蚕丝溶胀液： 将 98%甲酸用水稀释至 80%， 然后加入氯化钙配成含 2% 氯化钙的 80%甲酸溶液， 即为蚕丝溶胀液；
[0037] ( 2 ) 将桑蚕茧丝浸没于步骤 （1 ) 的溶胀液中 30s， 然后拉伸茧丝至原长的 2倍
， 得到拉伸茧丝；
[0038] ( 3 ) 步骤 （2 ) 得到的拉伸茧丝在去离子水洗涤后， 然后在 氢氧化钠水溶 液中和多余的酸， 再次水洗后置于 60°C烘箱中干燥得到高性能天然蚕丝纤维。
[0039] 表 2为处理前后茧丝的力学拉伸数据， 按本发明所提供的技术方案处理后的茧 丝具有优异的强度， 断裂强度达到 900MPa以上。
[0040] 表 2 处理前后茧丝的力学拉伸数据
[] [表 2] 样品 断裂强度 （MPa) 原茧丝 450 拉伸茧丝 920 [0041] 附图 3、 附图 4和表 2为上述高性能天然蚕丝纤维处理前后的红外谱图、 拉曼谱 图和力学性能。 由图 3可见， 处理后， 蚕丝内部的结晶度受到破坏， 与处理前相 比明显减小； 由图 4可见， 处理拉伸后， 蚕丝纤维的分子取向度显著提高； 有利 于天然蚕丝力学性能的提高。 此外， 由表 2可知， 拉伸处理后， 蚕丝的断裂强度 显著提高， 断裂强度达到 SOOMPa以上。
[0042] 实施例三
[0043] ( 1 ) 配制蚕丝溶胀液： 在 98%甲酸中加入硫氰酸锂配成含 1%硫氰酸锂的甲酸溶 液， 即为蚕丝溶胀液；
[0044] ( 2 ) 将 20-22D生丝浸没于步骤 （1 ) 的溶胀液中 50s， 然后控制茧丝收缩至原 长的 30%， 得到收缩生丝；
[0045] ( 3 ) 步骤 （2 ) 得到的收缩生丝在去离子水洗涤后， 然后在 lwt%氢氧化钠水溶 液中和多余的酸， 再次水洗后置于 70°C烘箱中干燥得到高性能天然蚕丝纤维。
[0046] 表 3为处理前后生丝的力学拉伸数据， 按本发明所提供的技术方案处理后的生 丝具有优异的延展性， 断裂伸长率达到 50%以上， 断裂功提高约 20%。
[0047] 表 3 处理前后生丝的力学拉伸数据
[] [表 3]
Figure imgf000007_0001
[0048] 实施例四
[0049] ( 1 ) 配制蚕丝溶胀液： 在 90%三氟乙酸中加入氯化镁配成含 1%氯化镁的氢氟酸 溶液， 即为蚕丝溶胀液；
[0050] ( 2 ) 将 20-22D生丝浸没于步骤 （1 ) 的溶胀液中 50s， 同时拉伸生丝至原长的 1
. 5倍， 得到拉伸生丝；
[0051] ( 3 ) 步骤 （2 ) 得到的拉伸生丝在去离子水洗涤后， 然后在 lwt%氢氧化钠水溶 液中和多余的酸， 再次水洗后置于 55°C烘箱中干燥得到高性能天然蚕丝纤维。
[0052] 表 4为处理前后生丝的力学拉伸数据， 按本发明所提供的技术方案处理后的生 [0053] 表 4 处理前后生丝的力学拉伸数据
[] [表 4]
Figure imgf000008_0001
[0054] 实施例五
[0055] (1) 配制蚕丝溶胀液： 将 98%甲酸稀释至 90%即为蚕丝溶胀液；
[0056] (2) 将直径约 0.22隱的蚕丝编织缝合线浸没于步骤 （1) 的溶胀液中 20s， 同 时拉伸编织缝合线至原长的 1.3倍， 得到拉伸编织缝合线；
[0057] (3) 步骤 （2) 得到的拉伸编织缝合线在去离子水洗涤后， 然后在 lwt%氢氧化 钠水溶液中和多余的酸， 再次水洗后置于 60°C烘箱中干燥得到高性能天然蚕丝 纤维。
[0058] 表 5为处理前后蚕丝编织缝合线的力学拉伸数据， 按本发明所提供的技术方案 处理后的拉伸编织缝合线断裂强力显著提高， 达到 3000cN以上。
[0059] 表 5 处理前后蚕丝编织缝合线的力学拉伸数据
[] [表 5]
Figure imgf000008_0002
[0060] 实施例六
[0061] (1) 配制蚕丝溶胀液： 将浓硫酸稀释至 30%即为蚕丝溶胀液；
[0062] (2) 将柞蚕丝浸没于步骤 （1) 的溶胀液中 50s， 然后拉伸至原长的 3倍， 然后 得到拉伸柞蚕丝；
[0063] (3) 步骤 （2) 得到的拉伸柞蚕丝在去离子水洗涤后， 然后在 lwt%氢氧化钠水 溶液中和多余的酸， 再次水洗后置于 60°C烘箱中干燥得到高性能天然蚕丝纤维 [0064] 表 6为处理前后柞蚕丝的力学拉伸数据， 按本发明所提供的技术方案处理后的 拉伸柞蚕丝断裂强力显著提高， 达到 lOOOMPa以上。
[0065] 表 6 处理前后柞蚕丝的力学拉伸数据
[] [表 6]
Figure imgf000009_0001
[0066] 实施例七
[0067] ( 1 ) 配制蚕丝溶胀液： 将浓磷酸稀释至 25%即为蚕丝溶胀液；
[0068] ( 2 ) 将蓖麻蚕丝浸没于步骤 （1 ) 的溶胀液中 30s， 然后拉伸至原长的 2倍， 得 到拉伸蓖麻蚕丝；
[0069] ( 3 ) 步骤 （2 ) 得到的拉伸柞蚕丝在去离子水洗涤后， 然后在 lwt%氢氧化钠水 溶液中和多余的酸， 再次水洗后置于 60°C烘箱中干燥得到高性能天然蚕丝纤维
[0070] 表 7为处理前后蓖麻蚕丝的力学拉伸数据， 按本发明所提供的技术方案处理后 的拉伸柞蚕丝断裂强力显著提高， 达到 780MPa以上。
[0071] 表 7 处理前后蓖麻蚕丝的力学拉伸数据
[] [表 7]
Figure imgf000009_0002
[0072] 本实施例的浓度都为质量浓度。 本发明对现有天然蚕丝纤维制品 （包括茧丝、 生丝、 捻线丝、 编织线等） 的后处理工序可以对其力学性能进行改造， 从而构 建出具有高性能、 高伸长的天然蚕丝纤维。

Claims

权利要求书
一种高性能天然蚕丝纤维的制备方法， 其特征在于， 包括以下步骤：
( 1 ) 制备蚕丝溶胀液， 所述蚕丝溶胀液包括酸与水；
( 2 ) 将天然蚕丝纤维放入上述蚕丝溶胀液中浸泡 1秒〜 1小时； 并对 天然蚕丝纤维进行收缩或者拉伸处理；
( 3 ) 将处理后的天然蚕丝纤维进行水洗、 中和处理， 再经水洗、 烘 干； 得到高性能天然蚕丝纤维。
根据权利要求 1所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （1 ) 中， 所述酸为甲酸、 三氟乙酸、 乙酸、 氢氟酸、 磷酸、 硫 酸中的一种或几种； 所述酸的浓度为 10〜99wt%。
根据权利要求 2所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （1 ) 中， 所述酸为甲酸、 氢氟酸、 磷酸、 硫酸中的一种； 所述 酸的浓度为 25〜98wt%。
根据权利要求 1所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （1 ) 中， 所述蚕丝溶胀液还包括无机盐； 所述无机盐为氯化钠 、 氯化钾、 溴化锂、 氯化钙、 氯化锌、 氯化镁、 硫氰酸锂、 硫氰酸钠 、 硫氰酸镁、 硝酸钙、 硝酸铜、 碳酸钙、 磷酸钙中的一种或几种； 所 述无机盐的浓度为 0. l〜10wt%。
根据权利要求 4所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （1 ) 中， 所述蚕丝溶胀液还包括无机盐； 所述无机盐为溴化锂 、 氯化钙、 氯化镁、 硫氰酸锂中的一种； 所述无机盐的浓度为 0. 5〜5 wt%。
根据权利要求 1所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （2 ) 中， 所述天然蚕丝为桑蚕丝、 柞蚕丝、 天蚕丝、 蓖麻蚕丝 中的一种或几种。
根据权利要求 1所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （2 ) 中， 所述天然蚕丝纤维为茧丝、 生丝、 捻线丝、 编织线中 的一种或几种的复合物。 [权利要求 8] 根据权利要求 1所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （2 ) 中， 所述收缩处理时的收缩率为 1〜80%； 所述拉伸处理时 的拉伸倍数为 1. 1〜5倍。
[权利要求 9] 根据权利要求 8所述高性能天然蚕丝纤维的制备方法， 其特征在于： 步骤 （2 ) 中， 所述收缩处理时的收缩率为 20〜70%； 所述拉伸处理时 的拉伸倍数为 1. 1〜3. 2倍； 浸泡时间为 5秒〜 5分钟。
[权利要求 10] 根据权利要求 1〜9所述任意一种高性能天然蚕丝纤维的制备方法制备 得到的高性能天然蚕丝纤维。
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