阅读说明：本技术 一种具有低表面张力的双重酯化淀粉浆料及其制备方法 (A kind of dual esterification starch slurry and preparation method thereof with low surface tension ) 是由 李伟 刘志 吴杰 吴兰娟 鲁育豪 阮芳涛 方寅春 刘倩 朱雨柯 张正桥 于 2019-08-23 设计创作，主要内容包括：本发明公开了一种具有低表面张力的双重酯化淀粉浆料的制备方法,属于纺织经纱上浆使用的改性淀粉浆料技术领域,本发明中首先对淀粉进行酸解降粘处理,增加其流动性,然后选择三聚磷酸钠和己酸酐为酯化剂,分别与酸解淀粉发生酯化反应,在淀粉大分子链上引入亲水性的磷酸基官能团和疏水性的己酸酯官能团,制备出一种具有低表面张力的双重酯化淀粉浆料。本发明所制备的改性淀粉浆料具有较低的表面张力,能大幅度提升淀粉浆液对纤维表面的润湿和铺展,从而实现改性淀粉浆料对聚乳酸等纤维具有高的粘着性能,改善浆纱质量和提高织造效率,并为纺织经纱上浆领域取代PVA奠定基础。(The preparation method of the invention discloses a kind of dual esterification starch slurry with low surface tension, belong to the modified starch paste technical field that textile warp starching uses, the processing of acidolysis viscosity reduction is carried out to starch first in the present invention, increase its mobility, then select sodium tripolyphosphate and caproic anhydride for esterifying agent, esterification occurs with acidified starch respectively, hydrophilic phosphate functional group and hydrophobic capronate functional group are introduced on starch polymer chain, prepare a kind of dual esterification starch slurry with low surface tension.Modified starch paste prepared by the present invention has lower surface tension, farinaceous size can significantly be promoted to the wetting of fiber surface and sprawled, to realize that modified starch paste has high adhesive performance to fibers such as polylactic acid, improve sizing quality and improve weaving efficiency, and replaces PVA to lay the foundation for textile warp starching field.)

1. a kind of preparation method of the dual esterification starch slurry with low surface tension, which is characterized in that specific step is as follows:

1) it weighs acidified starch and is scattered in the distilled water containing 1.1~4wt% sodium tripolyphosphate, be made form sediment after mixing evenly Powder cream, adjustment pH value of starch milk is 8-9, after electromagnetic agitation 20-50min, is filtered, by filter cake in 40-55 DEG C of baking oven It is warming up to 70-80 DEG C of baking 3-4h after preliminary drying 2-3.5h, then is warming up to 120-135 DEG C of baking 2-3h；

2) the product ethanol/water solution of volume ratio 1:1 will be dried to disperse, vacuum filtration, after washing 3 times, is dry, pulverize, mistake Sieve, is made phosphate ester starch；

3) phosphate ester starch is weighed, is distributed in isopropanol and is configured to starch milk, after mixing evenly, starch milk is poured into 1000mL Four-hole boiling flask in, be fixed in water-bath, adjusting pH value with diluted alkaline or weak brine solution under stirring is 8-9.5, is slowly added dropwise Caproic anhydride, and pH value 8-9.5, maintenance system reaction temperature 30- after completion of dropwise addition are maintained using above-mentioned diluted alkaline or weak brine solution 38 DEG C of the reaction was continued 0.5-1.5h, adjusting pH value with dilute acid solution after reaction is 6.5-7.0, is filtered, washing, and freezing is dry It is dry, it crushes, dual esterification starch slurry is made in sieving.

2. the preparation method of the dual esterification starch slurry according to claim 1 with low surface tension, feature Be: the mass concentration of the starch milk is 15~40%.

3. the preparation method of the dual esterification starch slurry according to claim 1 with low surface tension, feature Be: the dilute alkaline aqueous solution is the sodium hydrate aqueous solution of 1-2.5wt%, and weak brine solution is the sodium carbonate of 2-7wt% Solution, the dilute acid solution are the aqueous hydrochloric acid solution of 0.5-2mol/L.

4. the preparation method of the dual esterification starch slurry according to claim 1 with low surface tension, feature Be: the additional amount of the isopropanol is 1.5-6.4 times of starch quality.

5. the preparation method of the dual esterification starch slurry according to claim 4 with low surface tension, feature Be: the additional amount of the sodium tripolyphosphate is the 6% of starch quality.

6. the preparation method of the dual esterification starch slurry according to claim 1 with low surface tension, feature It is: a length of 20-80min when the dropwise addition of the caproic anhydride.

7. a kind of preparation side of the dual esterification starch slurry as described in any one of claim 1-6 with low surface tension Method, it is characterised in that: the additional amount of the caproic anhydride is the 3.75-15% of starch quality.

8. a kind of dual esterification starch slurry with low surface tension, which is characterized in that using any one of claim 7 institute The preparation method for stating the dual esterification starch slurry with low surface tension is prepared, described dual with low surface tension Phosphate functional group degree of substitution is 0.013 in esterification starch slurry, and capronate degree of substitution is 0.015-0.046, and total degree of substitution is 0.028-0.059。

Technical field

The invention belongs to starch size denaturation technique fields of weaving, and in particular to a kind of dual ester with low surface tension Change starch size and preparation method thereof.

Background technique

Warp yarn sizing is that it is resistance to improve its purpose is to increase through yarn intensity for one of critical process in textile weaving processes Performance is ground, its surface hairiness is reduced, the original elasticity of holding warp thread and extension at break mention to reduce weaving end breakage rate as far as possible High efficiency improves the quality of final products.

Sizing produces used slurry and belongs to a kind of dedicated adhesive, ensures that weaving production is normally carried out Key auxiliary agent.Slurry mainly includes starch, polyvinyl alcohol (PVA) class and polyacrylic acid (ester) class three categories, wherein starch The usage amount of slurry has been more than the 70% of total usage amount of above-mentioned three categories slurry.During textile sizing, in order to improve warp Yarn intensity and wear-resisting property are improved production efficiency and product quality with reducing end breakage, are usually starched using converted starch While material, it is necessary to use a large amount of PVA pulp components with.The performance for being primarily due to converted starch be not possible to fully meet through Yarn starching requirement, can only partially replace the usage amount of PVA.It is difficult to biodegrade in the natural environment in view of PVA, meeting is used for a long time Water ecological environment system is caused seriously to pollute, and PVA price is much higher than starch.Therefore improve starch performance, research and develop novel Modified starch size, to sizing quality is improved, save the cost is of great significance.Slurry is as a kind of dedicated adhesive, institute It is most important to the adhesiveness height of warp thread (fiber assembly) with it, after this adhesiveness is mainly reflected in slurry formation slurries It to fibroplastic adhesive effect, will be connected between fiber by this adhesive effect, to play increase through yarn intensity etc. Effect.It is well known that slurries will generate good adhesive effect to fiber, it is vital on condition that slurries will be to fiber surface It generates good wetting and sprawls.So setting about from farinaceous size is improved to the wetting of fiber surface and the effect of sprawling, improves and form sediment Powder size performance, and New Modified Starch slurry products are provided, there is important meaning to the sound development of entire sizing fabric industry Justice.

Summary of the invention

The technical problem to be solved by the present invention is to start with from the surface tension for reducing starch, providing one kind can reduce shallow lake The technological means of powder surface tension, wetting and sprawl effect of the Lai Gaishan farinaceous size to fiber surface, and one kind is invented whereby Dual esterification starch slurry with low surface tension and preparation method thereof, prepared dual esterification starch slurry form slurries Low surface tension is showed, will significantly improve wetting and sprawl effect of the farinaceous size to fiber surface, significantly improve shallow lake Powder improves loom production efficiency to the adhesive effect of fiber so as to improve sizing quality.

In order to solve the above technical problems, the present invention provides technical solution below:

A kind of preparation method of the dual esterification starch slurry with low surface tension, the specific steps are as follows:

1) it weighs acidified starch and is scattered in the distilled water containing 1.1~4.0wt% sodium tripolyphosphate, after mixing evenly Starch milk is made, adjustment pH value of starch milk is 8-9, after electromagnetic agitation 20-50min, is filtered, by filter cake at 40-55 DEG C 70-80 DEG C of baking 3-4h is warming up in baking oven after preliminary drying 2-3.5h, then is warming up to 120-135 DEG C of baking 2-3h；

2) the product ethanol/water solution of volume ratio 1:1 will be dried to disperse, vacuum filtration, after washing 3 times, dry, powder Broken, phosphate ester starch is made in sieving；

3) phosphate ester starch is weighed, is distributed in isopropanol and is configured to starch milk, after mixing evenly, starch milk is poured into It in the four-hole boiling flask of 1000mL, is fixed in water-bath, adjusting pH value with diluted alkaline or weak brine solution under stirring is 8-9.5, is delayed It is slow that caproic anhydride is added dropwise, and pH value 8-9.5 is maintained using above-mentioned diluted alkaline or weak brine solution, maintenance system reaction temperature after completion of dropwise addition 30-38 DEG C of the reaction was continued 0.5-1.5h of degree, adjusting pH value with dilute acid solution after reaction is 6.5-7.0, is filtered, washing, Freeze-drying crushes, and dual esterification starch slurry is made in sieving.

Preferably, the mass concentration of the starch milk is 15~40%.

Preferably, the dilute alkaline aqueous solution is the sodium hydrate aqueous solution of 1-2.5wt%, and weak brine solution is 2-7wt% Aqueous sodium carbonate, the dilute acid solution be 0.5-2mol/L aqueous hydrochloric acid solution.

Preferably, the additional amount of the isopropanol is 1.5-6.4 times of starch quality.

Preferably, the additional amount of the sodium tripolyphosphate is the 6% of starch quality.

Preferably, a length of 20-80min when the dropwise addition of the caproic anhydride.

Preferably, the additional amount of the caproic anhydride is the 3.75-15% of starch quality.

A kind of dual esterification starch slurry with low surface tension, using the above-mentioned dual esterification with low surface tension The preparation method of starch size is prepared, phosphate functional group in the dual esterification starch slurry with low surface tension Degree of substitution is 0.013, and capronate degree of substitution is 0.015-0.046, and total degree of substitution is 0.028-0.059.

It is that the present invention obtains the utility model has the advantages that

1, it uses sodium tripolyphosphate and caproic anhydride for esterifying agent, Phosphation and caproic acid esterification denaturation is carried out to starch respectively Processing introduces hydrophilic phosphate functional group and hydrophobic capronate functional group on starch molecular chain.It has found and passes through It introduces hydrophilic phosphate functional group and hydrophobic capronate functional group simultaneously, starch can be made to show and be substantially reduced Surface tension, and reduced surface tension will significantly improve farinaceous size to the wetting of fiber surface and the effect of sprawling, Starch is significantly improved to the adhesive effect of fiber, one kind is provided and improves it by reducing starch surface tension to fiber bonding The technological means of effect, the dual esterification starch slurry of invention not only have good adhesive effect, also with hydrophilic-hydrophobic Amphiphilic nature and excellent size film property.

2, the dual esterification starch slurry prepared by the present invention with low surface tension, by introducing hydrophily simultaneously and dredging Aqueous functional group makes starch have high surface-active, shows the surface tension being substantially reduced, significantly improve farinaceous size Wetting to fiber surface and the effect of sprawling significantly improve starch to the adhesive effect of fiber, so that the present invention is applicable not only to The starching of hydrophily warp thread (such as: cotton, fiber crops, viscose glue warp thread), and it is suitable for hydrophobicity warp thread (such as: pure polyester, polylactic acid Warp thread) starching.In addition, applying also for the starching of their mixed yarns.It is wide that warp thread variety range is applicable in starching, environmental protection, property The excellent feature of energy.

Detailed description of the invention

Fig. 1 is the surface tension test result figure of dual esterification starch slurries.

Fig. 2 is the X-ray diffraction analysis figure of dual esterification starch serous coat (a) and acidified starch serous coat (b).

Fig. 3 is the section electron scanning electron microscope of acidified starch serous coat (a) and dual esterification starch serous coat (b)

Fig. 4 is the electron scanning electron microscope of acidified starch particle (a) and dual esterification starch particle (b).

Fig. 5 is the infrared spectrogram of dual esterification starch, wherein curve a is dual esterification starch infrared spectrum curve, b For acidified starch infrared spectrum curve.

Specific embodiment

Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.