CN113463391B - Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof - Google Patents

Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof Download PDF

Info

Publication number
CN113463391B
CN113463391B CN202110817777.7A CN202110817777A CN113463391B CN 113463391 B CN113463391 B CN 113463391B CN 202110817777 A CN202110817777 A CN 202110817777A CN 113463391 B CN113463391 B CN 113463391B
Authority
CN
China
Prior art keywords
parts
starch
mixture
reaction
spandex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110817777.7A
Other languages
Chinese (zh)
Other versions
CN113463391A (en
Inventor
胡炳峰
李艳伟
陆水生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Huimei Starch Science & Technology Co ltd
Original Assignee
Guangdong Huimei Starch Science & Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Huimei Starch Science & Technology Co ltd filed Critical Guangdong Huimei Starch Science & Technology Co ltd
Priority to CN202110817777.7A priority Critical patent/CN113463391B/en
Publication of CN113463391A publication Critical patent/CN113463391A/en
Application granted granted Critical
Publication of CN113463391B publication Critical patent/CN113463391B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
    • 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
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a new warp sizing material for spandex core-spun yarns and a preparation method thereof, wherein the new warp sizing material for the spandex core-spun yarns comprises the following preparation raw materials in parts by weight: 100 parts of oxidized starch; 0-2 parts of 10% caustic soda; 0-1 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate; 3-5 parts of methyltetrahydrophthalic anhydride; 10-20 parts of betaine with the concentration of 60%; 5-10 parts of 10% ethylene glycol; 2-7 parts of water, wherein the content of both the caustic soda and the 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate is not 0. The new warp sizing material can completely replace PVA sizing agent, has good affinity with spandex filament, and has the excellent characteristics of good film forming property, good water solubility, good adhesion, easy desizing, complete biodegradation and the like.

Description

Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof
Technical Field
The invention belongs to the technical field of sizing agents for textile industry, and particularly relates to a new warp sizing material for spandex core-spun yarns and a preparation method thereof.
Background
The core-spun yarn is generally spun by using synthetic fiber yarn with good strength and elasticity as core yarn and twisting short fibers such as cotton, wool, viscose and the like outside the core yarn. The core-spun yarn has the excellent performances of both filament core yarn and short fiber covering. The common core-spun yarn is a spandex core-spun yarn which is a yarn made of spandex filament serving as a core yarn and other fibers coated outside the spandex filament, wherein the spandex filament has the characteristics of strong elasticity, high strength and fine fineness, but the spandex filament also has the defects of poor hygroscopicity, poor dyeing property, poor fabric appearance and the like. In the process of preparing the fabric from the yarns, the yarns are repeatedly rubbed, stretched and wound on a weaving machine, so that the yarns are easily broken and fluffed, the efficiency of the weaving machine and the quality of the fabric are affected, most of the yarns need to be subjected to warp sizing, and the fundamental purpose is to improve the weavability of the yarns and enable the yarns to bear strong mechanical action on the weaving machine in the weaving process. In the warp sizing process of the yarn, the slurry is coated on the surface of the warp and is partially wetted and permeated into the warp, so that the warp and the slurry are mutually bonded to form a slurry layer, the wear resistance of the warp is improved, the strength of the warp is increased, and the effect of attaching filoplume is achieved.
Conventional warp size includes polyvinyl alcohol (PVA), acrylic, modified starches. The polyvinyl alcohol sizing agent has good water solubility, cohesive force, film forming property and permeability, is ideal sizing agent, but has the defects of over-strong adhesion, difficult desizing, difficult yarn post-treatment, difficult biodegradation and serious environmental pollution, and has been prohibited from being used for textile sizing in foreign countries. The acrylic sizing agent has good water solubility and film forming property, and has better desizing and biodegradability than polyvinyl alcohol, but the acrylic sizing agent is easy to absorb moisture and re-stick, is often only used as an auxiliary material, and has high price and low cost performance. The modified starch is mainly used for textile sizing by using acidolysis powder and oxidation powder, has the advantages of rich raw materials, low price, easy obtainment, environmental protection and no pollution, but has the problems of aging and rising, hard and brittle pulp film, easy cracking and falling, and poor fiber wettability and adhesion, especially has insufficient affinity to synthetic fibers such as spandex, acrylon, polyvinyl chloride and the like, and can only be used as auxiliary pulp to be added into PVA. Compared with the conventional natural yarn, the spandex core-spun yarn has the characteristics of large elasticity, high elongation, easy resilience and the like, and the existing textile sizing process basically selects the matched combined sizing, such as PVA slurry, modified starch and the like, and takes PVA as main sizing, so that the problems of more hairiness of dry-twisted split yarn, difficult desizing and serious environmental pollution are solved although the wear resistance and the enhancement of the yarn are solved.
The invention develops a new warp sizing material suitable for the spandex core-spun yarn by deeply knowing the physical and chemical properties of the spandex core-spun yarn, can completely replace PVA sizing agents, has the excellent characteristics of good film forming property, good water solubility, good adhesion, easy desizing, complete biodegradation and the like, simplifies the existing sizing process, improves the workshop production environment, has practicability and environmental protection, and is suitable for wide popularization.
Disclosure of Invention
The invention aims to provide a new warp sizing material for spandex core-spun yarns, which can completely replace PVA sizing agents, has good affinity with spandex yarns, and has the excellent characteristics of good film forming property, good water solubility, good adhesion, easy desizing, complete biodegradation and the like.
The invention also aims to provide a preparation method of the new warp sizing material for the spandex core-spun yarn, the new warp sizing material prepared by the preparation method can completely replace PVA sizing agent, has good affinity with spandex, and has the excellent characteristics of good film forming property, good water solubility, good adhesion, easy desizing, complete biodegradation and the like.
In order to achieve the purpose, the invention provides a new warp sizing material for spandex core-spun yarns, which comprises the following raw materials in parts by weight:
100 parts of oxidized starch;
0-2 parts of 10% caustic soda;
0-1 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
3-5 parts of methyl tetrahydrophthalic anhydride;
10-20 parts of betaine with the concentration of 60%;
5-10 parts of 10% ethylene glycol;
2-7 parts of water;
wherein, the content of the caustic soda and the 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate are both different from 0.
Compared with the prior art, the carbon chain of the oxidized starch in the raw material for preparing the novel warp sizing material for the spandex filament core-spun yarn is based on glucose molecules, and hydroxyl groups on part of the glucose molecules in the oxidized starch are oxidized into carboxyl groups, so that the viscosity of the oxidized starch slurry is reduced, the fluidity is good, but the formed film is easy to crack and is not waterproof, the affinity to the spandex filament is general, and the bonding force of the slurry is insufficient, and if the oxidized starch slurry is directly applied to the warp sizing material of the spandex filament core-spun yarn, the requirements cannot be met, so that the raw material for preparing the novel warp sizing material for the spandex filament core-spun yarn further comprises caustic soda with the concentration of 10%, 3- (N, N-dimethyldodecylammonium) propane sulfonate, methyltetrahydrophthalic anhydride, betaine with the concentration of 60%, glycol with the concentration of 10% and water, and the film forming property of the oxidized starch and the affinity to the spandex filament are improved.
The reaction equation for the esterification of betaine with hydroxyl groups on oxidized starch is shown below:
Figure BDA0003171094910000032
the reaction equation of methyltetrahydrophthalic anhydride with hydroxyl groups on oxidized starch under alkaline conditions is shown below:
Figure BDA0003171094910000031
according to the two reaction equations, the betaine and the oxidized starch react to generate alkali, so that the pH value is continuously increased, the continuous increase of the pH value can inhibit the reaction, and the reaction efficiency is reduced; the reaction of the methyl tetrahydrophthalic anhydride and the oxidized starch consumes alkali, so that the pH value is continuously reduced, the continuous reduction of the pH value can promote the reaction, and the reaction efficiency is improved, therefore, the betaine and the methyl tetrahydrophthalic anhydride are mutually promoted in the same system, and the reaction efficiency of the esterification of the oxidized starch molecules, the methyl tetrahydrophthalic anhydride and the betaine can be improved; meanwhile, the caustic soda can activate the hydroxyl on the oxidized starch molecule, so that the oxidized starch molecule can easily react with the betaine and the methyl tetrahydrophthalic anhydride; the 3- (N, N-dimethyldodecylammonium) propane sulfonate has a hydrophobic nonpolar alkyl long carbon chain, and the nonpolar alkyl long carbon chain is beneficial to reducing the crystallinity of oxidized starch molecules so as to be beneficial to the esterification reaction of the oxidized starch molecules, methyl tetrahydrophthalic anhydride and betaine and improve the reaction rate; therefore, the esterification reaction of the oxidized starch molecules, methyl tetrahydrophthalic anhydride and betaine is accelerated, and the esterification substitution degree is higher, so that the novel warp sizing material has better film forming property and flexible sizing film.
In addition, the 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate also has hydrophilic sulfonic acid group and amino group, is easy to form adsorption on the surface of starch granules due to oily liquid, has the effect of moistening the starch granules, has the effect of reducing the crystallinity of the starch molecules, ensures that more hydroxyl groups on the starch molecules are easy to activate, ensures that more hydroxyl groups participate in the esterification reaction, ensures that the esterification substitution degree is slightly higher, and ensures that the serous membrane is more flexible; the ethylene glycol can neutralize unreacted methyl tetrahydrophthalic anhydride and can also perform esterification reaction with carboxyl on starch molecules, so that adjacent starch molecular chains are crosslinked, a net structure is formed, the flexibility of the size film is further improved, the size film is flexible, and the size film has good adhesion to spandex filaments, so that the affinity with the spandex filaments is facilitated. The methyl tetrahydrophthalic anhydride has a carbon chain with a proper length, the esterification reaction efficiency is high, the esterified starch has good film-forming property, and the cyclic structure contained in the methyl tetrahydrophthalic anhydride is similar to the cyclic structure in the hard carbon chain of the spandex filament, so that the methyl tetrahydrophthalic anhydride is further favorable for the affinity with the spandex filament according to the principle of similarity and intermiscibility. Therefore, the novel warp sizing material has the advantages of good film forming property, good flexibility and good affinity with spandex filaments.
Preferably, the oxidized starch of the present invention is prepared by oxidative denaturation of native starch.
In order to achieve the above object, the present invention also provides a method for preparing a new warp sizing material for spandex core-spun yarn, comprising the steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 0-2 parts of 10% caustic soda under stirring, adding 3-5 parts of methyltetrahydrophthalic anhydride, 0-1 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 10-20 parts of 60% betaine, and kneading for a certain time to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, carrying out microwave reaction at 90-120 ℃ and simultaneously dehumidifying to obtain a second mixture;
(3) Transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 2-7 parts of water and 5-10 parts of 10% ethylene glycol when the temperature is reduced to 50 ℃ or below, stirring for a certain time, and crushing to obtain a new warp sizing material;
wherein, the contents of the substances are calculated by weight parts, and the contents of the caustic soda and the 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate are not 0.
Compared with the prior art, the preparation raw materials comprise oxidized starch, the oxidized starch is easy to crack and is not waterproof when forming a film, the affinity to spandex is general, and the adhesion of the slurry is insufficient, and the addition of caustic soda, 3- (N, N-dimethyldodecylammonium) propane sulfonate, methyltetrahydrophthalic anhydride, betaine with the concentration of 60 percent, glycol with the concentration of 10 percent and water can improve the film forming property of the oxidized starch and the affinity to the spandex. In addition, the step (1) and the step (2) comprise the steps of carrying out microwave reaction on the oxidized starch, caustic soda, methyltetrahydrophthalic anhydride, 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate and betaine to enable the oxidized starch to be esterified and modified, namely the second mixture is esterified starch; the step (3) of the invention comprises the step of crosslinking the second mixture, namely the esterified starch, and the preparation method of the novel warp sizing material for the spandex core-spun yarn has strict operation requirements on the selection of raw materials and the addition sequence of the raw materials; secondly, the preparation method of the invention is that esterification reaction is carried out firstly, and crosslinking reaction is carried out only at the cooling stage after the esterification reaction, namely, the esterification and crosslinking have the sequential components, the esterification and crosslinking are carried out firstly, and then the crosslinking are carried out, because the methyltetrahydrophthalic anhydride can react with the glycol under the conditions of high temperature and microwave, the esterification degree of starch is further influenced, the glycol is added at the later stage of the reaction, the chemical property of the glycol is active, and the unreacted methyltetrahydrophthalic anhydride can be neutralized and consumed, so that the new warp sizing material can not be oxidized to generate acid in the placing process, the pH stability of the new warp sizing material is influenced, and the storage stability of the new warp sizing material is ensured; meanwhile, the glycol can also react with carboxyl generated by oxidation on the starch, and the dihydroxyl group carried by the glycol plays a certain crosslinking effect. Therefore, the novel warp sizing material prepared by the preparation method has good film forming property and good affinity with spandex filaments.
The reaction equation of ethylene glycol with carboxyl groups generated by oxidation on starch is as follows:
Figure BDA0003171094910000051
preferably, the kneading time in the step (1) is 30min, and the new warp sizing material is obtained by stirring for 15-30 min and crushing in the step (3).
Preferably, the step (1) of the present invention comprises adding 0-2 parts of 10% caustic soda under stirring, and adding methyl tetrahydrophthalic anhydride, 3- (N, N-dimethyldodecylammonium) propane sulfonate, and betaine after stirring for 5-10 min.
Preferably, the reaction conditions in step (2) of the present invention are: the microwave power is 10-20 kw, and the dehumidifying air quantity is 40-60 m 3 And/s, the reaction time is 40-60 min.
Preferably, the method for preparing oxidized starch of the present invention comprises:
(1) Uniformly stirring 100 parts of natural starch, 0-10 parts of 80% ethanol and 4-8 parts of 25% caustic soda solution, spraying 10-15 parts of 27% hydrogen peroxide and 0.5-4 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for a certain time to obtain a third mixture with the water content of 28-32%;
(2) And conveying the third mixture to a tunnel type microwave reactor for microwave oxidation and dehumidification, and cooling and crushing after the reaction is finished to obtain oxidized starch.
The caustic soda is a reactant of the alkalization reaction of the natural starch, has the functions of activating an internal active group of the starch to generate active hydroxyl, is a pH regulator of the oxidation reaction, is favorable for the oxidation reaction, and can cause the local gelatinization of the starch to influence the subsequent reaction when the using amount of the caustic soda exceeds a certain amount; ethanol is used as an organic solvent, has a certain effect of inhibiting starch gelatinization, can increase the using amount of caustic soda, does not participate in the reaction, and therefore, part of ethanol solution is added to inhibit the gelatinization of starch; copper sulfate plays a role of a catalyst in the reaction, the decomposition of hydrogen peroxide is accelerated, the catalytic efficiency is improved, and the reaction time is shortened, but the dosage is more than 0.05 percent, oxidized starch is slightly bluish, so the dosage is not suitable to be excessive, and black precipitates are generated with the added sodium hydroxide, so the copper sulfate cannot be added with caustic soda solution at the same time. The hydrogen peroxide and the copper sulfate are decomposed in the process of placing, bubbles are generated to escape, and the loss of the hydrogen peroxide is caused, so that the hydrogen peroxide and the copper sulfate can not be mixed and placed for a long time, and the hydrogen peroxide and the copper sulfate are mixed for use or atomized and sprayed respectively.
Preferably, the native starch of the present invention is selected from the group consisting of corn starch, tapioca starch, wheat starch, potato starch or waxy corn starch. It should be noted that different raw starches, different temperatures of the caustic soda solution, and different concentrations of caustic soda can all have some differences in the effect of starch gelatinization.
Preferably, the conveying of the third mixture to the tunnel type microwave reactor of the invention is as follows: and carrying the third mixed material by using a conveyor belt and continuously conveying the third mixed material to the tunnel type microwave reactor. The tunnel type microwave reactor is provided with a feeding hole and a discharging hole, the conveying belt penetrates through the feeding hole, the tunnel type microwave reactor and the discharging hole, the third mixture is placed on the conveying belt and enters the tunnel type microwave reactor through the feeding hole, and the third mixture is subjected to microwave reaction in the tunnel type microwave reactor. More specifically, the thickness of the third mix on the conveyor belt is 50 ± 2mm.
Preferably, the tunnel microwave reactor of the invention comprises a first section, a second section, a third section and a fourth section in sequence, the microwave power of the first section is 2kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 0-20 m 3 And s. Microwave heating makes starch molecules violently move to generate self-heating, the heating is simultaneously carried out inside and outside, compared with the heat conduction of a traditional oil furnace, the temperature rise is rapid, and the starch temperature of each part is equal.
Preferably, the reaction time of the third mixture in the tunnel microwave reactor is 45-60 min. Specifically, the speed of the conveyor belt can be controlled to ensure that the reaction time of the third mixed material in the tunnel type microwave reactor is 45-60 min.
Preferably, the step (1) of the method for preparing oxidized starch of the present invention comprises putting 100 parts of natural starch into a third kneader, adding 80% ethanol and 25% caustic soda solution during stirring, stirring at 25-35 ℃ for 20 minutes, and spraying 27% hydrogen peroxide and 0.01% anhydrous copper sulfate.
Preferably, the step (1) of the method for preparing oxidized starch of the present invention further comprises stirring and kneading for 20-30 min to obtain a third mixture with a water content of 28-32%.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
According to the invention, betaine, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (QUAB), 2,3-epoxypropyl trimethyl ammonium chloride (GTA) are respectively used as esterifying agents, natural starch and oxidized starch prepared by oxidizing and modifying natural starch are respectively used as raw materials, a microwave dry method is adopted to prepare cationic starch with a substitution Degree (DS) of about 0.08, the experimental conditions are shown in Table 1, and the experimental conditions are the same in each experimental group except for variables.
And (3) microwave dry method: adding starch into a first kneader, adding 10% caustic soda under stirring, adding 60% esterifying agent, and kneading for a certain time to obtain cationic starch.
The state of the starch after spraying the esterifying agent was observed and the initial pH of the starch was measured, and the results are shown in Table 2.
The degree of substitution was measured by the first Kjeldahl method of GB 5009.5-2016, and the results are shown in Table 2.
TABLE 1
Figure BDA0003171094910000081
As can be seen from Table 2, in the case of QUAB, when cationic starch with a Degree of Substitution (DS) of around 0.08 is prepared by microwave dry-method, the absolute dry mass ratio of native starch, QUAB to caustic soda is 100, and the pH of native starch is > 13, but when oxidized starch is used instead of native starch, the oxidized starch is gelatinized and cannot react after the injection of the esterifying agent. In the fifth group, the oxidized starch was not neutralized and its initial pH was alkaline, so that the amount of sodium hydroxide used was reduced when the initial pH of the oxidized starch was adjusted to 13.02.
As is clear from Table 2, it was found that the native starch after oxidation by spraying the esterifying agent had a reduced alkali resistance, i.e., when the amount of alkali added was too large, the oxidized starch was partially gelatinized at the time of initial contact. When the initial pH of the oxidized starch is controlled to < 11 by reducing the amount of alkali, neither QUAB nor betaine nor GTA will cause gelatinization of the oxidized starch.
As is clear from the results of the degree of substitution shown in Table 2, pH has an important influence on the reaction efficiency when QUAB and GTA are used as reagents. If GTA is used for esterification reaction, the dosage of sodium hydroxide can be greatly reduced, but the pH of the natural starch powder sample still needs to be more than 12 to have better reaction efficiency; oxidized starch is not tolerant to excessively high alkali content, so that the initial pH of the reaction (namely, the amount of sodium hydroxide is reduced) must be reduced, and although the oxidized starch is not aleurone, the reaction efficiency is greatly reduced; and when the betaine is applied to the oxidized starch as an esterifying agent, good reaction efficiency can be obtained when the reaction pH is 9-11, namely, the use amount of the alkali is small, the reaction efficiency is high, the alkali is not consumed in the reaction process, and the alkali is not required to be added in the middle of the reaction to maintain the stability of the pH. In addition, the betaine has smaller relative molecular weight than QUAB or GTA and more active chemical property, so the same cation substitution degree is obtained, the required medicament dosage is less, and the betaine does not contain chlorine ions, thereby avoiding the amide structure in spandex filaments from generating halogenation reaction with chlorine atoms to cause yellowing, strength reduction and elasticity reduction of the spandex filaments, and simultaneously, the textile wastewater does not contain AOX (absorbable halide) problem, thereby being more environment-friendly.
Secondly, the oxidized starch is respectively reacted with acetic anhydride, hexanoic anhydride and methyltetrahydrophthalic anhydride to generate esterified starch, wherein absolute dry mass ratios of the acetic anhydride, the hexanoic anhydride and the methyltetrahydrophthalic anhydride to the oxidized starch are all 5, and the substitution degree and the reaction efficiency of the generated esterified starch are calculated according to the following methods, and the results are shown in table 3.
Meanwhile, oxidized starch and prepared esterified starch are prepared into slurry with the concentration of 13%, the slurry is boiled for 1h at the temperature of 95 ℃, and then the slurry is subjected to a constant temperature and humidity test box with the temperature of 45 ℃ and the humidity of 65% to obtain a slurry film, and the state of the slurry film is shown in table 3. The serosa was then subjected to a double fold test, the results of which are shown in table 3.
And (3) calculating the degree of substitution: weighing 1.0000g of esterified starch in a beaker, adding 50ml of ethanol with volume fraction of 95%, magnetically stirring for 10min, adding 15ml of hydrochloric acid-ethanol solution with concentration of 2mol/L, magnetically stirring for 30min, transferring the oscillated sample into a sand core funnel, carrying out suction filtration, washing with 95% ethanol until no chloride ions exist (detected by 0.1mol/L silver nitrate), transferring the sample into a 250ml conical flask, adding 50ml of deionized water, dripping 3 drops of 1% phenolphthalein indicator, and dripping with 0.1mol/L sodium hydroxide until the color is reddish. Adding 25ml of 0.5mol/L sodium hydroxide, sealing, shaking for 30min, and saponifying. Titration with 0.2mol/LHCl standard solution until the red color disappears, the volume V1 consumed by the HCl standard solution is recorded, while the volume V2 consumed by the HCl standard solution is recorded using the unreacted powder as a blank.
Ester group content (w) = (V2-V1) × 0.2 × M/1000 × 100%;
degree of Substitution (DS) =162 × w/[ M × (100-w) ]; in the formula, M represents the molecular weight of an acid anhydride.
Calculating the reaction efficiency: reaction efficiency = degree of substitution/theoretical degree of substitution × 100%; wherein the theoretical degree of substitution = (5/M)/(100/162) =8.1/M, and M represents the molecular weight of the acid anhydride.
TABLE 3
Figure BDA0003171094910000101
The application of the anhydride in starch esterification can obviously improve the film forming property of starch. The anhydrides are generally formed by intermolecular dehydration reaction of two or more molecules of oxyacids, but the anhydrides with different carbon chain lengths have obvious differences in functions, the anhydrides with different carbon chain lengths are used for preparing the esterified starch with the same substitution degree, the longer the carbon chain of the anhydride is, the larger the newly formed ordered structure of the starch molecular chain after the esterification reaction is, the weaker the inter-chain and intra-chain hydrogen bond functions of the starch molecules, the larger the damage degree of the crystal structure of the starch is, the macroscopically shown esterified starch has better thermal stability, the better the flexibility of the prepared starch film, but the longer the carbon chain of the anhydride is, the steric hindrance effect is increased, the contact probability of the anhydride and hydroxyl on the starch chain is reduced, and the reaction efficiency is greatly reduced. As is clear from Table 3, an esterified starch having a degree of substitution of about 0.04, acetic anhydride (C), was prepared in the same manner 4 H 6 O 3 ) The reaction efficiency of (A) was about 91%, and the hexanoic anhydride (C) was 12 H 22 O 3 ) The reaction efficiency of the method is about 55 percent, the reaction efficiency of the methyltetrahydrophthalic anhydride is about 90 percent, a slurry film prepared from the acetic anhydride is similar to oxidized starch and has poor film forming property, the film forming property of the hexanoic anhydride is good but has poor toughness, and the slurry film prepared from the methyltetrahydrophthalic anhydride is flexible and complete and can be bent to a certain degree without breaking. Meanwhile, the methyl tetrahydrophthalic anhydride has a similar ring structure to that in a hard carbon chain of the spandex filament, and is favorable for affinity with the spandex filament according to the principle of similarity and intermiscibility. Therefore, methyltetrahydrophthalic anhydride was selected as the agent for the esterification reaction based on the overall reaction efficiency, slurry film state and practical use effect.
Thirdly, the addition of the 3- (N, N-dimethyldodecylammonium) propane sulfonate can enable the esterification substitution degree of the esterified starch to be slightly higher, a size film prepared by a new warp sizing material is more flexible, but the dosage is not too much, when the dosage exceeds 1.5%, the substitution degree is reduced, and the prepared size has too much foam, so the dosage is not more than 1%.
In addition, ethylene glycol is the smallest organic polyol, is the polyol with the most active chemical property compared with propylene glycol, butanediol and the like, is easy to perform esterification reaction with organic acid, can form ester groups with acid anhydride by both hydroxyl groups, has the highest reaction efficiency, and has the smallest molecular weight, so that the dosage of the reaction with the acid anhydride and carboxyl groups on starch is the smallest; if the reaction efficiency is low, the dosage needs to be increased and the temperature of the mixer needs to be raised (namely, the propylene glycol and the butanediol need to be atomized and sprayed when the temperature to be cooled is about 75 ℃), the temperature is higher at this moment, the sprayed medicament can enable part of powder to be pasted, the reaction efficiency is reduced, the mixer is polluted, the cleaning frequency is increased, continuous generation is hindered, and the generation efficiency is reduced, so that the selection of the ethylene glycol is the optimal selection, the dosage is the least, and the effect is the best. Meanwhile, water is sprayed into the powder in a mist manner at the temperature of 50 ℃ or below, the powder is not pasted and agglomerated, smooth powder discharging is ensured, and meanwhile, the moisture does not cause dust emission of a new warp sizing material due to too low moisture, so that the workshop production environment is improved.
According to the preparation method of the oxidized starch, the third mixture is conveyed to the tunnel type microwave reactor for microwave oxidation and dehumidification, water is an important factor in the microwave oxidation reaction, the water is beneficial to full contact between the medicament and the natural starch, and the reaction efficiency is high; however, excessive moisture can cause the powders to adhere to each other, which is not beneficial to the evaporation of the moisture, after the microwave reaction, the powders are gelatinized due to high temperature, but the reaction is prevented from further proceeding, and the prepared finished product has high moisture and serious agglomeration. When the water content is less, the medicament permeation is less, the reaction efficiency is low, the oxidation degree of the finished product is insufficient, and the subsequent reaction is influenced. The results of tests carried out under equivalent conditions with different moisture contents of corn starch are shown in table 4:
TABLE 4
Figure BDA0003171094910000121
As shown in the results in Table 4, the moisture content of the third mixture is greatly affected, and the moisture content of the third mixture should be controlled to be 28-32% in order to ensure that the native starch has a good oxidation effect.
Caustic soda solution with concentration of 25% and temperature of 25 ℃ was sprayed into different native starches, respectively, and the weight parts thereof when producing paste were as shown in table 5.
TABLE 5
Figure BDA0003171094910000122
Note: the corn starch source is Chinese food, the cassava starch source is Thailand ROI ET, the wheat starch source is Yihaijiali, the potato starch source is Ningxia Huaer crystal, and the waxy corn starch source is Qinhuang island Li Ye.
Different temperatures and different concentrations of caustic soda solutions were sprayed into the medium grain corn starch, and the weight parts of the resulting aleurone are shown in table 6.
TABLE 6
Figure BDA0003171094910000123
Figure BDA0003171094910000131
As can be seen from Table 6, the lower the caustic soda concentration, the lower the temperature, and the higher the amount added. However, in practical production, the concentration is low, and more water is brought into the starch, so that the powder is too wet to perform subsequent reaction. The reduction of the solution temperature needs extra cooling equipment to go on, all can not accord with the demand of actual production, consequently, selects 25% concentration's caustic soda solution relatively better.
The preparation method of the oxidized starch adopts a tunnel type microwave reaction process, and adjusts the microwave power and the dehumidifying power in a sectional manner, which combines the characteristics of the starch. Specifically, when starch initially enters the tunnel type microwave reactor, the moisture in the flour is high, and if the microwave power is too high, the temperature of the flour is rapidly increased to exceed the gelatinization temperature, so that the flour is pasted, and the reaction cannot be carried out, so that the microwave power is low in the initial stage, and the dehumidifying power is high, so that the moisture in the test flour can be rapidly escaped. After the moisture content is reduced to a certain degree, the microwave reaction power is improved to accelerate the reaction; when the moisture falls to a certain extent, the dissipation of the moisture is not favorable for the reaction, thereby reducing the dehumidifying power or turning off the dehumidifying. In actual production, in order to ensure the stability of quality, a temperature sensor is arranged in the middle of each section of microwave tunnel, temperature, humidity control monitoring and actual moisture detection statistics are carried out on the temperature sensor, the range of the temperature in each section of microwave reaction, humidity display data of the temperature and the range of the moisture content in the powder corresponding to the humidity display data are basically determined, and the table 7 shows the range.
TABLE 7
Figure BDA0003171094910000132
As can be seen from Table 7, in the first stage, when the temperature of the powder is 50-55 ℃, the content of carboxyl groups in the powder is low, and the water is dissipated more; in the second stage, when the temperature of the powder is between 60 and 65 ℃, the content of carboxyl in the powder is rapidly increased, and the water is rapidly dissipated; when the powder temperature in the third stage is between 60 and 70 ℃, the increasing speed of the carboxyl content of the powder is reduced, and the water dissipation speed is also reduced; after the fourth stage of microwave, the powder temperature further rises, but the increasing speed of the carboxyl content and the water dissipation speed are further slowed down, which indicates that the oxidation reaction is basically finished.
From the above, in the preparation process of the oxidized starch, the dosage of each raw material influences each other, for example, the increase of hydrogen peroxide is to obtain the oxidized starch with higher oxidation degree; in order to shorten the reaction time, it is necessary to add a little more copper sulfate catalyst. As the oxidation reaction proceeds, the pH of the starch decreases, which causes the reaction efficiency to decrease or even stop, and therefore, a little more sodium hydroxide needs to be added to maintain the pH of the reaction; however, the increase of sodium hydroxide may cause gelatinization of the powder due to excessive alkalinity, and therefore, an appropriate ethanol solution needs to be added to suppress the gelatinization. Thus, a change in the amount of any one raw material requires a corresponding change in the amount of the other raw material to ensure successful production of oxidized starch.
The new warp sizing material for spandex core-spun yarn and the method for preparing the new warp sizing material for spandex core-spun yarn of the present invention will be described in detail with reference to specific examples, in which all the raw materials are commercially available.
Example 1
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
0.5 part of caustic soda with the concentration of 10 percent;
0.5 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
5 parts of methyltetrahydrophthalic anhydride;
18 parts of betaine with the concentration of 60 percent;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch comprises the following steps of:
(1) Putting 100 parts of corn starch into a third kneader, adding 10 parts of 80% ethanol and 8 parts of 25% caustic soda solution in the stirring process, stirring for 20 minutes at 25 ℃, spraying 15 parts of 27% hydrogen peroxide and 4 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for 20 minutes to obtain a third mixture with the water content of 30%;
(2) Placing the third mixture on a conveyor belt, wherein the thickness of the third mixture is 50mm, conveying the third mixture to a tunnel type microwave reactor through the conveyor belt for microwave oxidation and dehumidification at the same time, cooling and crushing after reacting for 50min to obtain oxidized starch, wherein the tunnel type microwave reactor sequentially comprises a first section, a second section, a third section and a fourth section, the microwave power of the first section is 2kw, and the dehumidification air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 0m 3 /s；
The preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 0.5 part of 10% caustic soda under stirring, stirring for 8min, adding 5 parts of methyltetrahydrophthalic anhydride, 0.5 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 18 parts of 60% betaine, and kneading for 30min to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, carrying out microwave reaction at 120 ℃ and simultaneously dehumidifying to obtain a second mixture, wherein the microwave power is 15kw, and the dehumidifying air volume is 50m 3 The reaction time is 60min;
(3) And transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 4 parts of water and 8 parts of glycol with the concentration of 10% when the temperature is reduced to 50 ℃, stirring for 15min, and crushing to obtain a new warp sizing material.
The new material for warp sizing of example 1 was measured to be 13% concentration 13s using a YT821 funnel viscometer.
Example 2
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
1 part of caustic soda with the concentration of 10 percent;
1 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
4 parts of methyltetrahydrophthalic anhydride;
15 parts of 60% betaine;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch comprises the following steps of:
(1) Putting 100 parts of cassava starch into a third kneader, adding 6 parts of 80% ethanol and 6 parts of 25% caustic soda solution in the stirring process, stirring for 20 minutes at 25 ℃, spraying 12 parts of 27% hydrogen peroxide and 3 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for 20 minutes to obtain a third mixture with the water content of 28%;
(2) Placing the third mixture on a conveyor belt, wherein the thickness of the third mixture is 50mm, conveying the third mixture to a tunnel type microwave reactor through the conveyor belt for microwave oxidation and dehumidification at the same time, cooling and crushing after reacting for 50min to obtain oxidized starch, wherein the tunnel type microwave reactor sequentially comprises a first section, a second section, a third section and a fourth section, the microwave power of the first section is 2kw, and the dehumidification air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 20m 3 /s；
The preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 1 part of 10% caustic soda under stirring, stirring for 8min, adding 4 parts of methyltetrahydrophthalic anhydride, 1 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 15 parts of 60% betaine, and kneading for 30min to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, carrying out microwave reaction at 100 ℃ and simultaneously dehumidifying to obtain a second mixture, wherein the microwave power is 20kw, and the dehumidifying air volume is 60m 3 The reaction time is 60min;
(3) And transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 4 parts of water and 8 parts of glycol with the concentration of 10% when the temperature is reduced to 50 ℃, stirring for 15min, and crushing to obtain a new warp sizing material.
The new material for warp sizing of example 2 was measured at 13% concentration for 12s using a YT821 funnel viscometer.
Example 3
A new warp sizing material for spandex filament core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
2 portions of caustic soda with the concentration of 10 percent;
0.5 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
4 parts of methyltetrahydrophthalic anhydride;
15 parts of 60% betaine;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch comprises the following steps of:
(1) Putting 100 parts of potato starch into a third kneader, adding 5 parts of 80% ethanol and 6 parts of 25% caustic soda solution in the stirring process, stirring for 20 minutes at 25 ℃, spraying 10 parts of 27% hydrogen peroxide and 3 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for 20 minutes to obtain a third mixture with the water content of 31%;
(2) Placing the third mixture on a conveyor belt, wherein the thickness of the third mixture is 48mm, conveying the third mixture to a tunnel type microwave reactor through the conveyor belt for microwave oxidation and dehumidification at the same time, cooling and crushing after reacting for 50min to obtain oxidized starch, wherein the tunnel type microwave reactor sequentially comprises a first section, a second section, a third section and a fourth section, the microwave power of the first section is 2kw, and the dehumidification air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 20m 3 /s；
The preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 2 parts of 10% caustic soda under stirring, adding 4 parts of methyltetrahydrophthalic anhydride, 0.5 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 15 parts of 60% betaine after stirring for 5min, and kneading for 30min to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, performing microwave reaction at 110 ℃ and dehumidifying simultaneously to obtain a second mixture, wherein the microwave power is 15kw, and the dehumidifying air volume is 60m 3 The reaction time is 60min;
(3) And transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 4 parts of water and 8 parts of glycol with the concentration of 10% when the temperature is reduced to 50 ℃, stirring for 20min, and crushing to obtain a new warp sizing material.
The new material for warp sizing of example 1 was measured to be 13% concentration 13s using a YT821 funnel viscometer.
Example 4
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
0.9 portion of caustic soda with the concentration of 10 percent;
0.5 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
4 parts of methyltetrahydrophthalic anhydride;
15 parts of 60% betaine;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch comprises the following steps of:
(1) Putting 100 parts of waxy corn starch into a third kneader, adding 5 parts of 80% ethanol and 7 parts of 25% caustic soda solution in the stirring process, stirring for 20 minutes at 25 ℃, spraying 12 parts of 27% hydrogen peroxide and 4 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for 25 minutes to obtain a third mixture with the water content of 30%;
(2) Placing the third mixture on a conveyor belt, wherein the thickness of the third mixture is 52mm, conveying the third mixture to a tunnel type microwave reactor through the conveyor belt for microwave oxidation and dehumidification at the same time, cooling and crushing after reacting for 50min to obtain oxidized starch, wherein the tunnel type microwave reactor sequentially comprises a first section, a second section, a third section and a fourth section, the microwave power of the first section is 2kw, and the dehumidification air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 20m 3 /s；
The preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 0.9 part of 10% caustic soda under stirring, stirring for 10min, adding 4 parts of methyltetrahydrophthalic anhydride, 0.5 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 15 parts of 60% betaine, and kneading for 30min to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, carrying out microwave reaction at 120 ℃ and simultaneously dehumidifying to obtain a second mixture, wherein the microwave power is 15kw, and the dehumidifying air volume is 60m 3 The reaction time is 50min;
(3) And transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 4 parts of water and 8 parts of glycol with the concentration of 10% when the temperature is reduced to 50 ℃, stirring for 15min, and crushing to obtain a new warp sizing material.
The new warp sizing material of example 1 was measured to be 13% strength 12s using a YT821 funnel viscometer.
Example 5
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
1 part of caustic soda with the concentration of 10 percent;
1 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
3 parts of methyltetrahydrophthalic anhydride;
15 parts of 60% betaine;
7 parts of 10% ethylene glycol;
5 parts of water;
the preparation method of the oxidized starch comprises the following steps of:
(1) Adding 100 parts of wheat starch into a third kneader, adding 6 parts of 80% ethanol and 6 parts of 25% caustic soda solution during stirring, stirring for 20 minutes at 25 ℃, spraying 12 parts of 27% hydrogen peroxide and 3 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for 30 minutes to obtain a third mixture with the water content of 30%;
(2) Placing the third mixture on a conveyor belt, wherein the thickness of the third mixture is 50mm, conveying the third mixture to a tunnel type microwave reactor through the conveyor belt for microwave oxidation and dehumidification at the same time, cooling and crushing after reacting for 50min to obtain oxidized starch, wherein the tunnel type microwave reactor sequentially comprises a first section, a second section, a third section and a fourth section, the microwave power of the first section is 2kw, and the dehumidification air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 20m 3 /s；
The preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 1 part of 10% caustic soda under stirring, stirring for 5min, adding 3 parts of methyltetrahydrophthalic anhydride, 1 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 15 parts of 60% betaine, and kneading for 30min to obtain a first mixture;
(2) The first mix was transferred to a second kneader and micrometric at 120 ℃Performing wave reaction and dehumidifying simultaneously to obtain a second mixture, wherein the microwave power is 15kw, and the dehumidifying air volume is 50m 3 The reaction time is 50min;
(3) And transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 5 parts of water and 7 parts of glycol with the concentration of 10% when the temperature is reduced to 50 ℃, stirring for 15min, and crushing to obtain a new warp sizing material.
The new warp sizing material of example 1 was measured to be 13% strength 13s using a YT821 funnel viscometer.
Comparative example 1
Comparative example 1 a slurry of spandex core-spun yarn used in the prior art provided for a certain textile mill, the slurry formulation being: 50% of PVA +32% acid hydrolyzed powder +10% polyacrylate +8% emulsified oil.
The new warp sizing material of comparative example 1 was measured to be 13% concentration 13s using a YT821 funnel viscometer.
Comparative example 2
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
0.5 part of caustic soda with the concentration of 10 percent;
0.5 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
5 parts of methyltetrahydrophthalic anhydride;
18 portions of GTA with the concentration of 60 percent;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch and the preparation method of the new warp sizing material for the spandex core-spun yarn are completely the same as the example 1.
The new warp sizing material of comparative example 2 was measured to be 13% concentration 6s using a YT821 funnel viscometer.
Comparative example 3
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
0.5 part of caustic soda with the concentration of 10 percent;
0.5 part of 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate;
5 parts of acetic anhydride;
18 parts of betaine with the concentration of 60 percent;
8 parts of 10 percent ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch and the preparation method of the new warp sizing material for the spandex core-spun yarn are completely the same as those in the embodiment 1.
The new warp sizing material of comparative example 3 was measured to be 13% concentration 9s using a YT821 funnel viscometer.
Comparative example 4
A new warp sizing material for spandex core-spun yarns is prepared from the following raw materials in parts by weight:
100 parts of oxidized starch;
0.5 part of caustic soda with the concentration of 10 percent;
5 parts of methyltetrahydrophthalic anhydride;
18 parts of betaine with the concentration of 60 percent;
8 parts of 10% ethylene glycol;
4 parts of water;
the preparation method of the oxidized starch and the preparation method of the new warp sizing material for the spandex core-spun yarn are completely the same as the example 1.
The new warp sizing material of comparative example 4 was measured to be 13% in 10s using a YT821 funnel viscometer.
Comparative example 5
The preparation raw materials of a new warp sizing material for the spandex core-spun yarn are the same as those in the embodiment 1, and the preparation method of oxidized starch is also the same as that in the embodiment 1;
the preparation method of the new warp sizing material for the spandex core-spun yarn comprises the following steps of:
(1) Adding 100 parts of oxidized starch into a first kneader, adding 0.5 part of 10% caustic soda under stirring, adding 5 parts of methyltetrahydrophthalic anhydride, 0.5 part of 3- (N, N-dimethyldodecylammonium) propane sulfonate, 18 parts of 60% betaine and 8 parts of 10% ethylene glycol after stirring for 8min, and kneading for 30min to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, performing microwave reaction at 120 ℃ and dehumidifying simultaneously to obtain a second mixture, wherein the microwave power is 15kw, and the dehumidifying air volume is 50m 3 The reaction time is 60min;
(3) And transferring the second mixture into a mixer for stirring, atomizing and spraying 4 parts of water when the temperature is reduced to 50 ℃, stirring for 15min, and crushing to obtain a new warp sizing material.
The new warp sizing material of comparative example 5 was measured at 13% concentration for 7s using a YT821 funnel viscometer.
From the viscosities of the example 1 and the comparative example 2, the viscosity of the new warp sizing material for the spandex core-spun yarn in the example 1 is higher than that in the comparative example 2, and by combining the table 1 to the table 2, the esterification degree of the new warp sizing material for the spandex core-spun yarn finally obtained in the comparative example 2 is not high under the condition of not changing the alkali amount, macroscopically, the slurry with the same concentration is low in viscosity, and the prepared size film is easy to crack.
As can be seen from the viscosities of example 1 and comparative example 3, the viscosity of the new warp sizing material for spandex core-spun yarn of example 1 is higher than that of comparative example 3 because the carbon chain of the acetic anhydride molecule is very short, and after the acetic anhydride molecule reacts with oxidized starch, one end of the acetic anhydride molecule reacts with starch, and the other end of the acetic anhydride molecule is equivalent to a four-carbon tail formed on a starch glucose molecule, so that the length of the formed free carbon chain is very short, the displayed hydrophobicity is relatively weak, and the flexibility of the size film is poor; secondly, acetic anhydride is very acidic and active in chemical properties, and forms acetic acid after being dissolved in water, so that the initial pH of the test powder is reduced, and the esterification degree is further influenced. The esterification degree of the warp sizing new material for the spandex filament core-spun yarn finally obtained in the comparative example 3 is not high, the esterified free carbon chain is short, macroscopically, the viscosity of the serous fluid with the same concentration is low, and the prepared serous membrane is easy to crack.
It can be seen from the viscosities of example 1 and comparative example 4 that the new warp sizing material for spandex core-spun yarn in example 1 has a viscosity higher than that in comparative example 4, because the 3- ((N, N-dimethyldodecylammonium) propane sulfonate has both hydrophobic long carbon chains and hydrophilic sulfonic groups, and is an oily liquid, it is easy to form adsorption on the surface of starch particles, and has the effect of moistening starch particles, and has the effect of reducing the crystallinity of starch molecules, so that more hydroxyl groups on starch molecules are easy to activate, and more hydroxyl groups participate in the esterification reaction, and have the effect of increasing the degree of starch esterification.
As can be seen from the viscosities of example 1 and comparative example 5, the warp sizing new material for spandex filament core spun yarn of example 1 has a higher viscosity than comparative example 5 because ethylene glycol is sprayed into the powder together with tetrahydrophthalic anhydride, which first consumes part of the methyltetrahydrophthalic anhydride, resulting in a decrease in the degree of esterification and a decrease in viscosity; secondly, since the reaction can not be carried out completely by 100%, a small amount of methyltetrahydrophthalic anhydride residue is inevitably left after the reaction, and no ethylene glycol is neutralized, so that the pH stability of the test powder is reduced, and the test powder can not play a role in crosslinking, therefore, compared with example 1, the novel warp sizing material for spandex filament core-spun yarns obtained in comparative example 5 has a reduced esterification degree, macroscopically shows a reduced viscosity, and also has a reduced flexibility of a sizing film.
As can be seen from examples 1 to 5, the method for preparing the new warp sizing material for spandex filament core-spun yarns of the present invention has no selectivity for the type of natural starch, can arbitrarily select one of corn starch, tapioca starch, wheat starch, potato starch and waxy corn starch, and can be used to prepare the new warp sizing material by appropriately adjusting the ratio of the chemical, the reaction temperature and the reaction time.
The performance test of the new material of the invention in the aspect of sizing is carried out as follows, and the performance test specifically comprises a serous fluid and serous membrane test, a sizing state test, a sizing test and a trial production test.
Slurry and slurry film testing
The new warp sizing materials prepared in examples 1 to 5 and the size of comparative example 1 were tested for viscosity stability according to the following method, and the results are shown in Table 8. The slurries of examples 1 to 5 and comparative example 1 were made into a slurry film, after it was naturally dried to form a film, the film was cut into strips of 100mm long and 10mm wide, and the cut strips were placed in a constant temperature and humidity chamber, and after balancing for 24 hours, the tensile properties, water solubility and moisture absorption rate of the slurry film were measured as follows, and the results are shown in table 8.
Slurry viscosity stability: the slurry with the concentration of 6% is prepared according to the proportion of the examples 1-5 and the comparative example 1, the constant temperature water bath is heated and is continuously heated and stirred, when the temperature of the slurry rises to 95 ℃, the viscosity value is measured every 1h for 4 times, the ratio of the extreme difference of the viscosity value measured in the last 3 times to the viscosity value measured in the 1 st time is the viscosity fluctuation rate, and the viscosity stability =1 viscosity fluctuation rate (%).
The tensile property of the serous membrane is as follows: the balanced serosa strips were taken and subjected to a tensile strength test using an HM-K-30 tensile tester (Dongri instruments Co., ltd.), data was recorded, and an average value was taken 10 times in total.
Water solubility of the serous membrane: and (3) taking the balanced serous membrane strip, marking the middle of the serous membrane strip, then immersing the serous membrane strip into water at 50 ℃, ensuring that the mark is superposed with the water surface, starting timing until the serous membrane in the water falls off, recording the time, and taking an average value after 10 times of experiments. ( The water temperature of 50 ℃ is obtained according to actual experiments, when the water temperature is 80 ℃ or above, the time for dissolving the serosa is very short, only a few seconds exist, and effective distinguishing can not be carried out, and when the water temperature of about 25 ℃ is selected, the dissolving time is very long. Taking comparative example 1 as an example, it failed to dissolve in 30 minutes, which is not favorable for observation and test. Finally, the water temperature of 50 ℃ is selected for testing, the dissolution time is moderate, and the difference can be seen from each other. )
Moisture absorption rate of the size film: taking the balanced serous membrane strip, drying in an electrothermal blowing drying oven at 105 ℃ for 4h, weighing and recording as M1; and (5) putting the weighed serosa back into the constant temperature and humidity box to balance for 24 hours again, taking out and weighing, and recording as M2. Moisture absorption rate = (M2-M1)/M2 × 100%.
Table 8 test results of slurries and slurry films of examples 1 to 5 and comparative example 1
Figure BDA0003171094910000241
Figure BDA0003171094910000251
As can be seen from Table 8, the starch slurries prepared in examples 1 to 5 are good in viscosity heat stability, and substantially identical to comparative example 1; examples 1 to 5 were similar to comparative example 1 in breaking strength, but inferior to comparative example 1 in elongation, which indicates that the flexibility of the pulp film was still slightly insufficient compared to comparative example 1; the water solubility of the sizing films of examples 1-5 is better than that of comparative example 1, which shows that the novel warp sizing material of the invention is more soluble in water and easier to desize; the moisture absorption rates of the examples 1 to 5 are lower than that of the comparative example 1, which shows that the yarns after sizing are not easy to be sticky and difficult to be split. Therefore, the invention adopts a targeted modification mode to improve the fluidity, the adhesion and the film forming property of the starch, and the novel warp sizing material has the excellent characteristics of good film forming property, easy desizing, difficult re-adhesion and complete biodegradation.
Slashing condition test
The yarns of spandex/cotton (30/70) core-spun yarns are wound on an I-shaped iron frame in a stretched and straight manner (the yarns are not wound mutually, the iron frame is respectively immersed into the boiled serous fluid of the examples 1-5 and the comparative example 1, the soaked serous fluid is taken out after being soaked for 5 minutes, the soaked serous fluid is placed into an electric heating air blowing drying box to be dried, the yarns are cut off along the edge of the iron frame (the yarns in the contact part with the iron frame are abandoned), whether the yarns can maintain the shape and do not rebound is observed, if the yarns do not rebound, the yarn length before balance is measured, the yarns are placed into a constant temperature and humidity box to be balanced for 24 hours, the yarn length after balance is measured, and the yarn state after balance is that the yarn length after balance/the yarn length before balance is 100% (the average value of each group is obtained), and the results are shown in Table 9.
TABLE 9 sizing state results of examples 1 to 5 and comparative example 1
Figure BDA0003171094910000252
It can be seen from table 9 that the sizing agent of the new warp sizing material prepared in examples 1-5 can shape the spandex core-spun yarn, and the apparent effect is substantially close to that of comparative example 1, which shows that the new warp sizing material has good affinity with spandex filaments.
Sizing test
The new warp sizing material of example 1 and the size of comparative example 1 were prepared into a size with a mass fraction of 13%, sized using a single-yarn sizing machine of ASS3000 type, and tested for slashing abrasion resistance, slashing hairiness reduction, slashing reinforcement, slashing elongation reduction, and sizing percentage according to the following methods, and the results are shown in Table 10.
Sizing wear resistance and abrasion increase rate: testing the wear resistance of the slashing by using an MKY-Y731 type cohesion machine (Beijing Mac instrument), testing 30 groups at normal temperature, wherein the no-load round-trip speed is 100 times/min, recording data and calculating an average value;
A＝[(N1-N2)/N2]×100％
wherein A is the grinding increasing rate (%): n1 is the average wear-resisting times of slashing; p2 is the average abrasion resistance times of the base yarn.
Slashing hairiness reduction rate: carrying out yarn hairiness test by using a YG17B-2 type hairiness instrument (Changzhou middle fiber instrument), adjusting the instrument speed to 30m/min, testing the length of the yarn to be 10 meters each time, and recording the data of hairiness larger than 3mm to calculate the average value, wherein each group is 10 times;
B＝[(X1-X2)/X2]×100％
wherein B is a hairiness reduction ratio (%): x1 is the average hairiness number of sizing; x2 is the average hairiness number of the original yarn.
Sizing reinforcement and draw-down ratio: testing the yarn strength by using an HD021N type electronic single yarn strength instrument (Changzhou De Du Yiqi), adjusting the stretching speed of the instrument to 500mm/min, testing each group for 30 times in total, and calculating the average value;
c = [ (Y1-Y2)/Y2 ] x 100%
Wherein C is the reinforcement rate (%): y1 is slash breaking strength (cN); y2 is the base yarn breaking tenacity (cN).
D = [ (Z1-Z2)/Z2 ] x 100%
Wherein D is the elongation reduction rate (%); z1 is slash elongation at break (%); z2 is the raw yarn elongation at break (%).
And (3) sizing rate test: respectively taking 10m sized yarn and 10m raw yarn, drying the yarn and the raw yarn at the temperature of 105 ℃ in an oven to constant weight, and cooling. Weighing M1 and M2 with an analytical balance (Saedolis BSA224S type), recording data until the data is accurate to 0.1mg, and repeating 10 groups to obtain an average value;
e = [ (M1-M2)/M1 ]. Times.l 00% (3)
Wherein E is a sizing percentage (%); m1 and M2 are respectively the mass of the slashed yarn and the element after drying and cooling.
TABLE 10 sizing test results for example 1 and comparative example 1
Index (I) Comparative example 1 Example 1
Abrasion increasing ratio (%) 645.3 581.2
Hairiness reduction (%) 82.4 91.3
Fracture reinforcing Rate (%) 14.6 17.8
Elongation percentage (%) 7.1 4.5
Sizing percentage (%) 12.2 12.5
As can be seen from table 10, the slashing effect of the new warp sizing material prepared in example 1 is substantially close to that of comparative example 1, and is slightly better than that of comparative example 1 in terms of attaching hairiness and reducing stretch, and application trial can be performed.
Trial production
The new material size for warp sizing prepared in example 1 was tried in a textile mill and compared to the existing process of comparative example 1 and the results are shown in table 11.
Table 11 trial run results of example 1 and comparative example 1
Figure BDA0003171094910000271
From the trial production results in table 11, the new warp sizing material of the invention is suitable for spandex filament core-spun yarns, basically meets the actual production requirements, is a relatively ideal PVA textile sizing material substitute product, has good affinity with spandex filaments, has the excellent characteristics of low-temperature sizing, good film forming property, good water solubility, good adhesion, easy desizing and complete biodegradation, simplifies the existing sizing process, improves the workshop production environment, has practicability and environmental protection, and is suitable for wide popularization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of a new warp sizing material for spandex core-spun yarns is characterized by comprising the following steps:
(1) Putting 100 parts of oxidized starch into a first kneader, adding 0~2 parts of 10% caustic soda under stirring, adding 3~5 parts of methyltetrahydrophthalic anhydride, 0~1 parts of 3- (N, N-dimethyldodecylammonium) propane sulfonate and 10-20 parts of 60% betaine, and kneading for a certain time to obtain a first mixture;
(2) Transferring the first mixture into a second kneader, carrying out microwave reaction at 90-120 ℃ and simultaneously carrying out dehumidification to obtain a second mixture;
(3) Transferring the second mixture into a mixer, stirring and cooling, atomizing and spraying 2-7 parts of water and 5-10 parts of 10% ethylene glycol when the temperature is reduced to 50 ℃ or below, stirring for a certain time, and crushing to obtain a new warp sizing material;
wherein, the contents of the above substances are calculated by weight parts, and the contents of the caustic soda and the 3- (N, N-dimethyl dodecyl ammonium) propane sulfonate are not 0.
2. The method for preparing the new material for sizing the warp yarn of the spandex core-spun yarn according to claim 1, wherein the kneading time in the step (1) is 30min, and the stirring time in the step (3) is 15 to 30min.
3. As claimed in claim 1The preparation method of the new warp sizing material for the spandex core-spun yarn is characterized in that the reaction conditions in the step (2) are as follows: the microwave power is 10 to 20kw, and the dehumidifying air volume is 40 to 60m 3 And/s, the reaction time is 40 to 60min.
4. The method for preparing a new material for warp sizing of spandex core-spun yarn according to claim 1, wherein the method for preparing oxidized starch comprises:
(1) Uniformly stirring 100 parts of natural starch, 0-10 parts of 80% ethanol and 4~8 parts of 25% caustic soda solution, spraying 10-15 parts of 27% hydrogen peroxide and 0.5-4 parts of 0.01% anhydrous copper sulfate, and stirring and kneading for a certain time to obtain a third mixture with the water content of 28-32%;
(2) And conveying the third mixture to a tunnel type microwave reactor for microwave oxidation and dehumidification, and cooling and crushing after the reaction is finished to obtain the oxidized starch.
5. The method for preparing a new material for sizing warp yarn of spandex filament covering yarn according to claim 4, wherein the natural starch is selected from corn starch, tapioca starch, wheat starch or potato starch.
6. The method for preparing the new warp sizing material for the spandex core-spun yarn according to claim 4, wherein the step of conveying the third mixture to the tunnel microwave reactor comprises the following steps: and carrying the third mixed material by using a conveyor belt and continuously conveying the third mixed material to the tunnel type microwave reactor.
7. The method for preparing the new material for sizing warp of spandex core-spun yarn as claimed in claim 4, wherein the tunnel type microwave reactor comprises a first section, a second section, a third section and a fourth section in sequence, the microwave power of the first section is 2kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the second section is 4kw, and the dehumidifying air volume is 40m 3 S; the microwave power of the third section is 4kw, and the dehumidifying air volume is 20m 3 S; the microwave power of the fourth section is 4kw, and the dehumidifying air volume is 0-20m 3 /s。
8. The method for preparing the new material for sizing the warp yarn of the spandex core-spun yarn as claimed in claim 4, wherein the reaction time of the third mixture in the tunnel type microwave reactor is 45-60min.
9. The new material for sizing warp prepared by the method for preparing the new material for sizing warp of spandex filament core-spun yarn in any one of claims 1~8.
10. The new material for warp sizing according to claim 9, wherein said oxidized starch is obtained by oxidative denaturation of native starch.
CN202110817777.7A 2021-07-20 2021-07-20 Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof Active CN113463391B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110817777.7A CN113463391B (en) 2021-07-20 2021-07-20 Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110817777.7A CN113463391B (en) 2021-07-20 2021-07-20 Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113463391A CN113463391A (en) 2021-10-01
CN113463391B true CN113463391B (en) 2023-02-03

Family

ID=77881263

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110817777.7A Active CN113463391B (en) 2021-07-20 2021-07-20 Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113463391B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6037466A (en) * 1998-12-31 2000-03-14 National Starch And Chemical Investment Holding Corporation Method for preparing hydrophobic starch derivatives
FI20030769A0 (en) * 2003-05-21 2003-05-21 Raisio Chem Oy Starch derivatives, their preparation and use
EP2079762B1 (en) * 2005-12-08 2012-10-03 Chemigate Oy A process for the preparation of hydroxy polymer esters and their use
CN101880335B (en) * 2010-02-03 2012-05-23 内蒙古奈伦农业科技股份有限公司 Method for preparing modified starch by oxidation and succinic anhydride esterification

Also Published As

Publication number Publication date
CN113463391A (en) 2021-10-01

Similar Documents

Publication Publication Date Title
CN103266536B (en) Preparation method and use of paper surface sizing agent
CN101476245B (en) Textile slurry composition mixed with starches of different denaturation degrees and preparation thereof
Shen et al. Preparation and characterization of oxidized sesbania gum and evaluation of its warp sizing performance for fine cotton yarns
CN101463563A (en) Modified starch/polyacrylamide textile slurry composition and preparation thereof
Li et al. Quaternization/maleation of cornstarch to improve its adhesion and film properties for warp sizing
CN103898755B (en) A kind of spinning sizing agent being applicable to dacron
CN105064028B (en) DTY low elastic polyester filament starching water-soluble polyurethanes and preparation method thereof
CN103342754A (en) Method for preparing modified starch and application of modified starch
CN105001345A (en) Ionic liquid solution of palmitate modified starch sizing agent and application thereof
CN113463391B (en) Novel warp sizing material for spandex filament core-spun yarn and preparation method thereof
CN112301505A (en) Seamless down-filled down jacket fabric and production method thereof
CN115679474A (en) Hydrolysis-resistant polylactic acid fiber composite material and preparation method thereof
CN103030700A (en) Compound modified starch and preparation method and application thereof
JPS62280201A (en) Fiber size
CN103898752A (en) Textile size applicable to high-count cotton fabrics
Li et al. Effect of sulfosuccinylation of corn starch on the adhesion to viscose fibres at lower temperature
CN102718878A (en) Preparation method and application of oxidized starch
CN108691239B (en) Preparation method and application of composite modified corn starch flame-retardant material
CN103898756B (en) A kind of method for sizing being applicable to dacron spinning sizing agent
CN105646860B (en) A kind of slurry of unsaturated polyester (UP) containing end carboxyl and its preparation technology
CN109056322A (en) Crosslinked starch sizing agent, preparation method and the application of chitin fiber
CN111218845A (en) Method and device for preparing sizing glue solution
Zhu et al. Electroneutral cornstarch by quaternization and sulfosuccinylation to improve the adhesion of cold starch paste to raw cotton for low-temperature sizing
CN111575826A (en) Fluorine-containing polyester fiber and preparation method thereof
CN111395034A (en) cCS-PAE binary composite reinforcing agent and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant