阅读说明：本技术 基于α螺旋与β折叠转变的潜性高膨体细化羊毛及其制备 (Latent high-bulked refined wool based on alpha helix and beta sheet transformation and preparation thereof ) 是由 刘洪玲 于伟东 赵亮 刘刚中 张国生 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种基于α螺旋与β折叠转变的潜性高膨体细化羊毛及其制备方法。制备方法为：将羊毛纤维置于预处理液中,打开羊毛纤维大分子链中二硫键和盐式键的交联；对羊毛纤维进行拉伸,使羊毛分子内部结构由α螺旋向β折叠转变；对羊毛纤维即时定型,使α螺旋段暂时稳定在β折叠态,即伸直态。本发明采用的α螺旋与β折叠转变的潜性高膨体细化羊毛,对超短羊毛或羊绒纤维的高附加值利用有良好的效果。(The invention discloses a latent high-bulked refined wool based on alpha helix and beta sheet transformation and a preparation method thereof. The preparation method comprises the following steps: putting the wool fibers into pretreatment liquid, and opening the cross-linking of disulfide bonds and salt bonds in the macromolecular chains of the wool fibers; stretching the wool fiber to convert the internal structure of the wool molecule from alpha helix to beta folding; the wool fibers are shaped in time to temporarily stabilize the alpha helical section in a beta-folded state, i.e., an extended state. The high-expansion thinned wool with the alpha helix and beta folding transformation has good effect on high added value utilization of ultrashort wool or cashmere fibers.)

1. A preparation method of potential high bulkiness refined wool based on alpha helix and beta sheet transformation is characterized by comprising the following steps:

step 1): putting the wool fibers into pretreatment liquid, and opening the cross-linking of disulfide bonds and salt bonds in the macromolecular chains of the wool fibers;

step 2): stretching the wool fiber to convert the internal structure of the wool molecule from alpha helix to beta folding;

step 3): the wool fibers are shaped in time to temporarily stabilize the alpha helical section in a beta-folded state, i.e., an extended state.

2. The method of claim 1, wherein the wool fibers are replaced with alpaca, mohair, rabbit hair, or cashmere.

3. The method of claim 1, wherein the pretreatment solution in step 1) comprises sodium bisulfite, thioglycolic acid, a surfactant, triethanolamine, and an EDTA salt.

4. The method according to claim 1 or 3, wherein the pretreatment liquid in the step 1) has a mass concentration of 1 to 5%.

5. The method according to claim 1, wherein the diameter of the drawn wool fiber in step 2) is reduced by 10 to 20%, the diameter of the drawn wool fiber is reduced by 2 to 4 μm, the strength of the drawn wool fiber is increased by 15 to 30%, and the crimp elastic modulus of the drawn wool fiber is not less than 50%.

6. The method of claim 1, wherein the drawing speed in the step 2) is maintained at 100%/min.

7. The method of claim 1, wherein the wool fiber obtained in step 3) has a shrinkage of not less than 30% after boiling water treatment, and is a potentially high bulk refined wool.

8. The latent high texturized wool based on alpha helix and beta sheet transition produced by the method for producing latent high texturized wool based on alpha helix and beta sheet transition according to any one of claims 1 to 7.

Technical Field

The invention relates to a method for researching a thinning mechanism of wool fibers, in particular to potential high-bulked thinned wool based on alpha helix and beta sheet transformation and preparation thereof.

Background

Wool is an important textile raw material, has the characteristics of good elasticity, good heat retention, strong hygroscopicity, difficult contamination, soft luster and the like, is a material for various high-grade clothes and rare ornaments, and is also widely applied to fabrics in various seasons with strong heat retention. In recent years, with the increase of demand for living quality, wool fabrics having both warmth retention and lightness and thinness have become popular with consumers, and therefore lightness and thinness of wool fabrics have become an important research direction, and reduction of fineness by stretching and thinning is a scientific and effective solution. The boiling water shrinkage rate of the existing wool refining material is generally 12% -40%, namely the main mechanism of the stretching refinement is caused by the transformation from an alpha spiral macromolecular structure to a beta folding macromolecular structure, and through a stretching test, the slow elastic section on the wool stretching curve disappears, generally 0% -3%, the fiber becomes rigid, the integral breaking elongation of the fiber is only 10% -13%, so that the strength of the fiber is not more than 20%, and the fineness of the fiber is not more than 5.5 μm or more than 26%.

Many studies on wool fibers have been carried out, mainly focusing on the following aspects:

the first category relates to the process of wool stretch refining. A knitting yarn of wool draw and thin color spinning A70-648s/2 and its processing technology (patent application No. 201110291393.2) adopts the immersion reduction softening agent, twisting composite drawing technology and permanent shaping technology for 56s short wool, and utilizes the principle that the alpha helical structure is converted into beta folding structure. A technology for drafting and thinning wool (201210389495.2) features that the colloid is used to coat wool for drafting by one time at most according to the easily broken wool in its stretching process. A method for stretch refining and non-permanent shaping of colored and uncolored wool (patent application No. 201310326438.4; 201310326437.X) comprises stretch refining colored or colorless wool having a fineness of 14.7-28.0 μm to a non-permanent shape of 12.7-22.7 μm, and then shrinking the wool under a wet heat condition of 90 ℃ or higher. A method of stretch refining and permanent setting of uncolored wool (patent application No. 201310326446.9) is also to refine wool of the above-mentioned fineness to 12.7 μm to 22.7 μm, and unlike the non-permanent setting, the refined wool is given a set and the strength of the wool can be increased by 20%. The maximum stretching amount of the stretching and thinning process is 100 percent, and the principle is based on the conversion of an alpha helical structure to a beta folding structure, the slippage of a molecular layer is not achieved, and the method is far from the invention.

The second type is the reagent formulation used for wool refining. The chemical treatment agent for wool stretching (patent application No. 01112860.7), the setting treatment agent for refined wool stretching (patent application No. 01112859.3), the multifunctional setting agent and setting process for refined wool stretching (patent application No. 200410024653.X) and the chemical treatment agent for wool stretching and setting (patent application No. 01112858.5) are mainly used in the formula of the chemical treatment agent for the wool stretching and refining treatment process. However, the formulation used in the present invention is very different from the aforementioned formulations. Although the formula can stretch wool, the slippage on the molecular layer surface is not easy to achieve in the stretching process, and stable superfine wool is not easy to form. The invention can further obtain the structural change in the wool fiber stretching process, and obtain the superfine wool by adjusting the relationship among the twist, the drafting speed and the holding distance.

The third type relates to a method for manufacturing a machine dedicated to the fine stretching. A wool top thinning, twisting and stretching test apparatus (patent application No. 200810053074.6) mainly passes through the experimental model and means of stretching wool under the wet and hot condition, the diameter of the wool thinning given in the example is reduced by 3.3 μm or 15% at most. A wool draw false twisting device with a heat pipe (patent application No. 200720018151.5) is a device for improving the false twisting degree and the drawing fineness of wool fibers by utilizing the heat resources of a factory. A wool stretching and setting device and a wool stretching and setting process (patent application number: 201510366668.2) provide the wool stretching and setting device and the wool stretching and setting process, the setting process is wet-heat setting (the temperature is 80-100 ℃ and the relative humidity is 90-100%), the stretching times are not mentioned in the patent, and only the strip discharging speed is limited. A wool stretching auxiliary agent blending and conveying device (patent application number: 201420296122.5) only realizes blending and conveying of auxiliary agents and does not relate to the principle and process of stretching and refining. A wool continuous stretching device (application number: 201420434896.X) is mainly used for the continuous production of the wool by physical refining, and a specific refining method and stretching times are not given in the patent. The maximum theoretical stretching ratio of the special machine (patent application number: 200410025087.4) for thinning and stretching wool and various animal fibers (or fabrics) is 70%. The special stretching machines of the types have the outstanding characteristics of low stretching and thinning rate and difficult formation of superfine wool. Compared with the present invention, the invention principle provided by the present invention is completely different from the above examples, and the stretching and thinning degree is greatly improved, and the thinning effect is far better than that of the above materials.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the existing wool refining materials still have the defect of low refining efficiency.

The invention aims to solve the problems that: temporarily stretching the wool fibers to stabilize the microstructure in a beta-sheet structure, thereby preparing the high-bulked refined wool with the potential.

In order to solve the technical problems, the invention provides a preparation method of potential high-bulked refined wool based on alpha helix and beta sheet transformation, which is characterized by comprising the following steps of:

step 1): putting the wool fibers into pretreatment liquid, and opening the cross-linking of disulfide bonds and salt bonds in the macromolecular chains of the wool fibers;

step 2): stretching the wool fiber to convert the internal structure of the wool molecule from alpha helix to beta folding;

step 3): the wool fibers are shaped in time to temporarily stabilize the alpha helical section in a beta-folded state, i.e., an extended state.

Preferably, the wool fibres are replaced by alpaca, mohair, rabbit hair or cashmere.

Preferably, the pretreatment solution in step 1) includes sodium bisulfite, thioglycolic acid, a surfactant, triethanolamine, and an EDTA salt.

Preferably, the mass concentration of the pretreatment solution in the step 1) is 1-5%.

Preferably, the diameter of the stretched wool fiber in the step 2) is thinned by 10-20%, the diameter of the wool fiber is thinned by 2-4 μm, the strength of the wool fiber is increased by 10-30%, and the crimp elastic rate of the wool fiber is not less than 50%.

Preferably, the drawing speed in said step 2) is maintained at 100%/min.

Preferably, the shrinkage rate of the wool fiber obtained in the step 3) after the treatment with boiling water is not less than 30%, namely the latent high-bulked refined wool.

The invention also provides the latent high bulked refined wool based on the alpha helix and beta sheet transformation, which is prepared by the preparation method of the latent high bulked refined wool based on the alpha helix and beta sheet transformation.

The evaluation mechanism of the present invention is based on the following:

the wool can be stretched and refined by the molecular structure of the wool, the structure of the wool microfibril is formed by adding a circle of 9 basic fibrils and two middle basic fibrils, the basic fibrils are generally considered to be formed by 3 helices or 2+2 repeated helices of macromolecules, the macromolecules are bonded together through disulfide bonds, the disulfide bonds among the macromolecules can be completely opened through a chemical method, and the slippage among the macromolecules can be generated by stretching. In the process of producing yarn, the drawing and thinning of the top or roving are caused by slippage between fibers. However, the macromolecules are not only bonded together by disulfide bonds, but also salt bonds, hydrogen bonds, and van der waals forces are present. The average length of every three amino acid residues in the wool fiber isThus, the average length of each α amino acid residue is

When the fiber is stretched by drawing, the molecular arrangement can be converted into β folded structure with repeating unit length

From the peptide chain structure, the length of the repeating molecular chain can be calculated, and the straightening times of the molecular chain when the secondary structure of wool is changed from α type to β type are as follows:

the results indicate that the maximum stretching multiple of the wool fiber is 93% if the wool fiber is converted only from the α -helical structure to the β -sheet structure during the refining process.

In fact, it is impossible and not desirable for the wool fibers to completely convert the α -helical structure into the β -sheet structure during the thinning process. As an impossibility, one is that there is no possibility of a complete alpha helical conformation in the fiber, but that there are alpha, non-alpha and beta structures; secondly, the network cross-linking structure will cause part of the alpha structure to be unable to transform into beta structure. The X-ray diffraction results show that the transformation of alpha structure to beta structure always occurs in the wool fibers in the yield zone and the strengthening zone (Bendit E G.A qualitative X-ray diffraction basis of the alpha-beta transformation in wood fiber. textileRes. J.,1960,30(8): 547-555); thirdly, the defects and weak nodes of the fiber structure can not realize the alpha-beta transformation of an ideal perfect structure (Yu W, Postle R, Yan H. geological and mechanical characteristics of the week-points of wood fibers, Pro.6th ATC. hong Kong.2001-08-22-24.4). As an unforeseeable principle, firstly, the properties of the fibers are different, the respective stretching multiples are different, and the requirement of the theoretical stretching multiple cannot be met on the whole; secondly, after the alpha structure is completely converted into the beta structure, the molecular structure of the refined wool is unstable, and the beta structure can be partially retracted into the alpha structure under the damp and hot condition, so that the refining effect is difficult to stabilize.

Therefore, it is found from the above analysis that the elongation cannot be more than 93% in order to realize the transformation between the α -helix and the β -sheet.

The prepared high-bulkiness thinned wool can be used for processing high-bulkiness slivers and fabrics of worsted wool spinning.

The invention provides a method for stretching and refining wool fibers with superfine rate by combining conversion from alpha helix to beta sheet structure and partial slippage and refining.

Compared with the prior art, the invention has the beneficial effects that:

(1) by adopting a rapid stretching method, the effective time for converting the alpha helix to beta folding can be shortened, and the shaping is more facilitated;

(2) a one-step sizing process is adopted, so that chemical bonds such as disulfide bonds and the like in the wool are fixed, but no crosslinking is formed between spiral chains, and the recovery of potential high elasticity is facilitated;

(3) the invention has wide application range and can be used for the processing technology of high added value of wool short velvet, cashmere short velvet and fibrilia.

Drawings

FIG. 1 is a drawing of a wool fiber stretching and setting mechanism;

FIG. 2 is an electron micrograph of wool having an elongation of 80%. Please provide corresponding embodiments

Detailed Description

In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.