CN103059225B - The production method of grafting modified starch sizing agent - Google Patents
The production method of grafting modified starch sizing agent Download PDFInfo
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- CN103059225B CN103059225B CN201210527982.0A CN201210527982A CN103059225B CN 103059225 B CN103059225 B CN 103059225B CN 201210527982 A CN201210527982 A CN 201210527982A CN 103059225 B CN103059225 B CN 103059225B
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Abstract
The invention discloses a kind of production method of grafting modified starch sizing agent, first processor for ultrasonic wave is adopted to carry out ultrasonic pretreatment to ative starch breast, acrylic acid or the like mixed grafting monomer is added subsequently in system, insert glow-discharge electrode, carry out glow discharge, the graft copolymerization in initiator system, powered-down, maintenance temperature of reaction system is 35-50 DEG C, polyreaction 2-3h, obtains the graft starch loosened.Under glow discharge technique effectively can realize cold condition, initiation grafting reacts, and elicitation procedure temperature controls steadily, and product graft rate is higher.Ultrasonic pretreatment and glow discharge technique have less energy-consumption, it is little to pollute, and the treatment time is short, the feature of successful, makes the production process of graft starch become a kind of clean, environmental protection process efficiently.
Description
Technical field
The invention belongs to field of textiles, the production method of the grafting modified starch of particularly a kind of yarn sizing.
Background technology
Denim belongs to a thick high density fabric, and thread count coefficient is high, and the fabric compactness coefficient of heavy pound denim is more than 100%.The requirement of denim cloth cover is smooth, lines is clear, for reaching this effect, will adopt hightension, thwack latitude technique when weaving, and the shuttleless weaving machine how fast in speed, tension force is large is weaved.In addition, warp thread is first through dyeing before weaving for denim, and this process is not little to the damage of yarn, needs to make up through sizing.Warp sizing is one of critical process of denim production, warp yam surface is made to be coated to smooth, wear-resisting, the pliable and tough serous coat with some strength of one deck by starching, make part size infiltrate the inside of yarn simultaneously, increase interfibrous adhesive power, improve the tensile strength of yarn, frictional strength and subsides volt filoplume, so reach reduce weave end breakage rate, the object of quality product of enhancing productivity, improve.
It is with a long history that starch is used for warp sizing, ative starch has good adhesivity to hydrophilic natural fiber, there is certain film forming ability, substantially the starching requirement of natural fiber can be met, but its sizing performance still can not be of great satisfaction, often need to add various auxiliary slurry and made up or carry out denaturing treatment.Ative starch slurry, to the poor adhesion of synthon, therefore adopts modified starch more.Three generation products is gone through in the development of modified starch, and first on behalf of starch-splitting, and it is to cut off the glucoside key on starch polymer, reduces the polymerization degree and viscosity, and increase working concentration and water dispersible are main purpose, and product comprises acidified starch, Sumstar 190 etc.Second on behalf of starch derivative, introduces some chemical group in starch molecule, to improve the water dispersible of slurries, gel resistance, plasma membrane properties and clinging power for main purpose, as etherification starch, esterification starch and cationic starch etc.The first-generation and s-generation modified starch can add the affinity of starch to yarn to a certain extent, improve adhesive power and the stability improving slurries.Graft starch is third generation product, graft starch normally adopts vinyl monomer to be caused the synthesis polymer side chain being formed on starch polymer main chain and have certain polymerization degree by radical, this product has native starch and the high molecular dual property of synthesis, synthesis macromolecular chain part serves as connection component in slurry mix, and the flexible molecule chain of bonding significantly can improve the toughness of serous coat.Graft starch itself has two-phase laminated flow structure, significantly improves the mechanical property of starch.Due to the advantage that these are potential, add good biodegradability, graft starch causes the very big concern of textile limit in recent years.
Domestic graft starch many employings Acrylic Acid Monomer graft process, is polymerized the graft starch obtained, warp sizing is not only possessed the high-performance of starch size, also has the tack good to hydrophobic fibre that other modified starch sizes do not have.Concerning warp sizing, graft starch can improve starch use value, is considered to the best slurry of substitution for PVA.
But, the starch graft copolymer reaction of producing grafting modified starch sizing agent is carry out in the mode of radical polymerization mostly, most free radical reaction adopts chemical process to cause, be initiator mainly with high price cerium ion, high price cerium ion is expensive, limits throughput, as slurry, textile industry demand is large, and this constrains the development of grafting modified starch sizing agent undoubtedly; Meanwhile, the polyreaction of chemistry initiation, the percentage of grafting of product, generally about 10%, is difficult to make graft product thoroughly break away from the weakness of starch size.
Summary of the invention
The object of the invention is to overcome jean yarn starching adopts starch to be the shortcoming that main body slurry and graft starch exist in process of production, a kind of production method of graft starch of applicable jean yarn starching is provided, the employing of this production method is ultrasonic carries out pre-treatment to ative starch, utilize glow discharge physics to cause starch and acrylic acid-grafted graft copolymerization subsequently, form acrylic acid grafted starch slurry.
The invention provides a kind of production method of grafting starch, it comprises the steps:
1) use in NaOH and vinylformic acid, preparing propone acid sodium solution, the vinyl monomer being 30-40% by obtained sodium acrylate solution and concentration mixes, obtained mixed monomer solution;
2) common starch is added deionized water furnishing starch milk, normal temperature is transferred in processor for ultrasonic wave, supersound process 15-25min, obtained supersonic modifying ative starch breast;
3) obtained supersonic modifying ative starch breast is transferred in glow discharge reactor, in starch milk, pass into N
2, in reaction system, add the mixed monomer solution containing vinyl, insert glow-discharge electrode, carry out glow discharge under room temperature, the graft reaction in initiator system;
4) keep temperature of reaction system to be 35-50 DEG C, polyreaction 2-3h, filter washing, obtain the graft starch loosened, by dry for graft starch, pulverize, sieve after obtain grafting starch.
Wherein, described common starch comprises any one in W-Gum, yam starch, wheat starch, tapioca (flour).
Wherein, the ultrasonic frequency of processor for ultrasonic wave used is 40kHz, and temperature is 40-50 DEG C, and starch milk mass concentration is 30-40%.
Wherein, the sparking voltage of glow discharge initiator system is 500-800V, and discharging current is 100-150mA, and glow discharge time is 1-5min.
Wherein, the monomer used of the mixed monomer solution containing vinyl comprises at least one in vinylformic acid, vinyl cyanide, methyl acrylate, ethyl propenoate, butyl acrylate.
The grafting starch that the present invention produces is compared with traditional slurry, and its advantage is as follows:
1) the present invention adopts ultrasonic wave to carry out pre-treatment to ative starch, and the method operating procedure is simple, and do not add extra chemical reagent, the treatment time of production process starch is short, energy consumption is low, therefore production process be environmental protection process.
2) the present invention adopts contacting glow technology to cause starch polymer and forms free radical, instead of the scarcity metals cerium salt of the costliness that traditional chemical elicitation procedure adopts, be conducive to reducing product cost, strengthen the production output of graft starch, accelerate the rapid popularization of grafting starch.The method is simple, and initiation reaction at ambient temperature, be conducive to the graft reaction of polymkeric substance, decrease the self-polymeric reaction of mix monomer, improve monomer-grafted efficiency.Causing under cold condition makes polyreaction operational stability good, is conducive to controlling monomer-grafted rate, from but the product stability of graft starch is good.
3) graft starch production method suitability of the present invention is comparatively wide, and different polymerization single polymerization monomers to be starch-graftedly polymerized with dissimilar, can produce and be suitable for cotton textiles, wash/starching the requirement of cotton blending yarn.
4) grafting starch that the present invention produces is applied in the starching of jean yarn, can substitute traditional combined slurry with single slurry, and the complexity before thoroughly solving traditional starching is sized mixing process, shortens starching process period.
Embodiment
The present invention is complicated for allocating when solving the application of jean yarn sizing material, and propose to adopt and ultrasonic pre-treatment is carried out to ative starch, utilize glow discharge physics to cause starch and acrylic acid-grafted novel process subsequently, polymerization generates grafting starch directly can substitute the starching of conventional combination slurry for jean yarn.
So-called starch ultrasonic pretreatment mainly utilizes ultrasonic cavitation to produce high temperature locally, high pressure (5500 DEG C and 100 MPa) and high-frequency vibration, the molecular chain generating portion of starch polymer is degraded, molecular weight reduces, and starch particle diameter diminishes simultaneously, is conducive to the viscosity reducing starch paste.There is the cellular hole that degree is different or crackle in the starch particle surface after supersound process, the infiltration being conducive to reaction reagent is immersed.
So-called starch-grafted novel process utilizes contacting glow technology to process modified starch emulsion at ambient pressure, caused in the solution by the electrode inserted in solution and generate starch polymer free radical, subsequently with pass into system acrylic acid or the like mix monomer and carry out graft polymerization reaction.Obtain energy (average energy is 100eV) after the positive ion of the gasification produced in glow discharging process accelerates under the effect of highfield, clash into, at the H of excited state with the water molecules of starch emulsion
2o
+ *with H
2there is Charger transfer in the collision process of O and produce hydroxyl radical free radical (OH) and hydroperoxyl radical (H), shown in 1-4.
Hydroxyl radical free radical (OH) and hydroperoxyl radical (H) are the high energy particles of contacting glow system, move to bulk solution further, react with the starch polymer in solution under the effect of strong electrical forces.Be generally living radical and capture hydrogen in starch molecule on hydroxyl carbon atom, the hydrogen especially on C2 or C3 atom, produce Starch Free Radicals, as shown in Equation 5.
Starch Free Radicals causes acrylic monomer generation transfer reaction again, until chain termination, C2 or the C3 atom of starch polymer accesses acrylic polymers side chain, as shown in Equation 6.
Below in conjunction with formulation examples, the present invention is specifically described.
Embodiment 1
NaOH solution is joined in vinylformic acid, control the pH to 5-7 of solution, preparing propone acid sodium solution.Using obtained sodium acrylate solution with 35% acrylic acid solution that contains mix as grafted monomer mixture, wherein sodium acrylate and acrylic acid molar ratio are 1:6.Potato common starch is added the starch milk of deionized water furnishing starch-containing 30%, normal temperature is transferred in processor for ultrasonic wave, is warming up to 50 DEG C, opens ultrasonic insulation 25 min, obtained supersonic modifying starch milk.Starch milk is transferred in glow discharge reactor, in starch milk, pass into N
210min, slowly stirs simultaneously and the temperature of reaction system is down to room temperature.Mixed monomer solution is added in proportion, wherein the mass ratio 70:10 of starch milk and mixed monomer solution in reaction system.Electrode insertion, switch on power after continuing slowly to stir 20min, control voltage is 600V, and electric current is that 100mA carries out glow discharge 1min, the graft reaction in initiator system, powered-down.Slow intensification, keeps temperature of reaction system to be 40 DEG C, polyreaction 2h.Filtering washing, obtaining the graft starch loosened, through pulverizing and sieving obtained grafting starch.The percentage of grafting of this grafting starch is 16.6%, and monomer-grafted efficiency is 66.8%.This stock quality concentration is 6%, and when gelatinization point is 90 DEG C, the viscosity of dextrin is 11.4cp, viscosity stability >=90%.
By 120 parts, above-mentioned slurry, butter 4 parts of Homogeneous phase mixing, add in the size cooking pan containing 1000kg soft water, and the mashing off that heats up after stirring 10min is to boiling, and be incubated 20 min, adding 95 DEG C of hot water is 1250kg to volume, namely can be used for 16
s× 21
sthe starching of jean yarn.
Embodiment 2
NaOH solution is joined in vinylformic acid, control the pH to 5-7 of solution, preparing propone acid sodium solution.Using obtained sodium acrylate solution with 35% the vinylformic acid that contains mix as grafted monomer mixture with the solution of butyl acrylate (vinylformic acid and butyl acrylate mol ratio 10:1), wherein sodium acrylate and acrylic acid molar ratio are 1:8.Common corn starch is added the starch milk of deionized water furnishing starch-containing 35%, normal temperature is transferred in processor for ultrasonic wave, is warming up to 45 DEG C, opens ultrasonic insulation 25 min, obtained supersonic modifying starch milk.Starch milk is transferred in glow discharge reactor, in starch milk, pass into N
2oxygen in displacement system, slowly stirs simultaneously and the temperature of reaction system is down to 25 DEG C.Mixed monomer solution is added in proportion, wherein the mass ratio 90:10 of starch milk and mixed monomer solution in reaction system.Electrode insertion, switch on power after continuing slowly to stir 20min, control voltage is 600V, and electric current is that 100mA carries out glow discharge 1min, the graft reaction in initiator system, powered-down.Slow intensification, keeps temperature of reaction system to be 40 DEG C, polyreaction 2h.Filtering washing, obtaining the graft starch loosened, through pulverizing and sieving obtained grafting starch.The percentage of grafting of this grafting starch is 19.4%, and monomer-grafted efficiency is 70.4%.This stock quality concentration is 6%, and when gelatinization point is 90 DEG C, the viscosity of dextrin is 12.6cp, viscosity stability >=90%.
By 120 parts, above-mentioned slurry, butter 3 parts of Homogeneous phase mixing, add in the size cooking pan containing 1000kg soft water, and the mashing off that heats up after stirring 10min is to boiling, and be incubated 10 min, adding 95 DEG C of hot water to volumes is 1250kg, namely can be used for the starching of heavy pound jean yarn.
Embodiment 3
NaOH solution is joined in vinylformic acid, control the pH to 5-7 of solution, preparing propone acid sodium solution.Using obtained sodium acrylate solution with 30% the vinylformic acid that contains mix as grafted monomer mixture with the solution of vinyl cyanide (mol ratio 10:0.5), wherein sodium acrylate and acrylic acid molar ratio are 1:6.Potato common starch is added the starch milk of deionized water furnishing starch-containing 30%, normal temperature is transferred in processor for ultrasonic wave, is warming up to 50 DEG C, opens ultrasonic insulation 25 min, obtained supersonic modifying starch milk.Starch milk is transferred in glow discharge reactor, in starch milk, pass into N
210min, slowly stirs simultaneously and the temperature of reaction system is down to 25 DEG C.Mixed monomer solution is added in proportion, wherein the mass ratio 80:20 of starch milk and mixed monomer solution in reaction system.Electrode insertion, switch on power after continuing slowly to stir 20min, control voltage is 600V, and electric current is that 100mA carries out glow discharge 1min, the graft reaction in initiator system, powered-down.Slow intensification, keeps temperature of reaction system to be 40 DEG C, polyreaction 2h.Filtering washing, obtaining the graft starch loosened, through pulverizing and sieving obtained grafting starch.The percentage of grafting of this grafting starch is 17.9%, and monomer-grafted efficiency is 64.3%.This stock quality concentration is 6%, and when gelatinization point is 90 DEG C, the viscosity of dextrin is 14.3cp, viscosity stability >=90%.
Adopt slurry manufactured by production method of the present invention at sizing process without the need to other auxiliary agents, easy to operate, can basically eliminate denim aftertreatment slurry pollution on the environment.Wherein, under glow discharge technique effectively can realize cold condition, initiation grafting reacts, and elicitation procedure temperature controls steadily, and product graft rate is higher.Ultrasonic pretreatment and glow discharge technique have less energy-consumption, it is little to pollute, and the treatment time is short, the feature of successful, makes the production process of graft starch become a kind of clean, environmental protection process efficiently.
Although the present invention illustrates with reference to embodiment and describes, will be understood by those skilled in the art that, when not departing from the spirit and scope of the present invention that the appended claims limit, the various changes of form and details can be carried out.
Claims (2)
1. a production method for grafting modified starch sizing agent, it comprises the steps:
1) use in NaOH and vinylformic acid, preparing propone acid sodium solution, the vinyl monomer being 30-40% by obtained sodium acrylate solution and concentration mixes, obtained mixed monomer solution, wherein vinyl monomer comprises at least one in vinylformic acid and vinyl cyanide, methyl acrylate, ethyl propenoate, butyl acrylate;
2) common starch being added deionized water furnishing mass concentration is the starch milk of 30-40%, and normal temperature is transferred in processor for ultrasonic wave, and control ultrasonic frequency is 40kHz, and temperature is 40-50 DEG C, supersound process 15-25min, obtained supersonic modifying ative starch breast;
3) obtained supersonic modifying ative starch breast is transferred in glow discharge reactor, N2 is passed in starch milk, the mixed monomer solution containing vinyl is added in reaction system, insert glow-discharge electrode, carry out glow discharge under room temperature, sparking voltage is 500-800V, and discharging current is 100-150mA, glow discharge time is 1-5min, the graft reaction in initiator system;
4) keep temperature of reaction system to be 35-50 DEG C, polyreaction 2-3h, filter washing, obtain the graft starch loosened, by dry for graft starch, pulverize, sieve after obtain grafting starch.
2. the production method of grafting modified starch sizing agent according to claim 1, is characterized in that: described common starch comprise in W-Gum, yam starch, wheat starch, tapioca (flour) any one.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557533A (en) * | 2004-01-16 | 2004-12-29 | 上海蓝景膜技术工程有限公司 | Low-temperature plasma grafting infiltration vaporization membrane and its preparing method |
| CN101353393B (en) * | 2008-09-12 | 2010-12-08 | 东华大学 | Grafting starch having improved lateral branch construction, clean preparation and use thereof |
| CN101560280B (en) * | 2009-06-02 | 2011-04-13 | 湖北省农业科学院农产品加工与核农技术研究所 | Method for preparing binary-graft starch by irradiation initiation |
| CN102051015A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Ultrasound microwave method for synthesizing methyl acrylate grafted starch slurry |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557533A (en) * | 2004-01-16 | 2004-12-29 | 上海蓝景膜技术工程有限公司 | Low-temperature plasma grafting infiltration vaporization membrane and its preparing method |
| CN101353393B (en) * | 2008-09-12 | 2010-12-08 | 东华大学 | Grafting starch having improved lateral branch construction, clean preparation and use thereof |
| CN101560280B (en) * | 2009-06-02 | 2011-04-13 | 湖北省农业科学院农产品加工与核农技术研究所 | Method for preparing binary-graft starch by irradiation initiation |
| CN102051015A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Ultrasound microwave method for synthesizing methyl acrylate grafted starch slurry |
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