Starch-based warp size and preparation method thereof

Abstract

The invention relates to the technical field of size for the textile industry, and provides starch-based warp size and a preparation method thereof.The starch-based warp size is prepared from 30-50 parts of starch, 1-1.5 parts of supported sodium percarbonate, 0.2-0.5 part of O-25, 0.4-2 parts of ethylene glycol distearate, 0.3-0.5 part of sodium carbonate and 350-500 parts of water; and further comprises 0.03 to 0.6 part of ammonium persulfate. According to the starch-based warp size provided by the invention, the sized warp has high wear resistance by controlling a starch oxidation technology, and meanwhile, the sizing percentage of the warp can be reduced.

Description

Technical Field

[0001] This invention relates to the field of sizing technology for the textile industry, and particularly to a starch-based warp sizing solution and its preparation method. Background Technology

[0002] Warp sizing is a crucial step in the textile weaving process. Its purpose is to form a tough, flexible, and highly adhesive sizing film on the warp yarn surface, thereby improving the yarn's abrasion resistance, fuzziness, and tensile strength, thus meeting the demanding conditions of high-speed weaving. Traditional sizing agents mainly include three categories: starch, polyvinyl alcohol (PVA), and polyacrylates. Among these, starch-based sizing agents are the most widely used in the textile industry due to their advantages of wide availability, low price, good biodegradability, and excellent adhesion to cellulose fibers.

[0003] While starch-based sizing agents offer numerous advantages, pure starch sizing agents also possess inherent drawbacks. For instance, the natural starch molecular chain, composed of numerous glucose units linked by α-1,4 glycosidic bonds, exhibits a rigid cyclic structure and high degree of polymerization, leading to a brittle and hard sizing film and consequently insufficient abrasion resistance in the sized yarn. To address these issues, the industry primarily modifies starch through chemical modification (such as oxidation, esterification, and etherification) or by adding auxiliaries (such as softeners and emulsifiers) to improve its film-forming properties, flexibility, and adhesion, thereby enhancing the abrasion resistance of the sized yarn. Oxidized starch is one of the most widely used modified varieties. Existing technologies mostly employ single oxidants such as sodium hypochlorite, hydrogen peroxide, and sodium percarbonate to modify starch, but these methods may suffer from insufficient stability and unsatisfactory oxidation effects.

[0004] Patent CN 101519455B discloses a method for preparing composite modified starch, which includes adding an oxidant to oxidize and modify starch paste. The oxidant used is sodium monochloride. The modified starch is then applied to warp sizing. This method has the advantages of low cost and easy desizing. However, this invention does not consider the problem that using a single oxidant results in insufficient oxidation efficiency and can easily lead to brittle sizing film and poor abrasion resistance.

[0005] Therefore, there is an urgent need in the market for a starch-based warp sizing solution that can improve the abrasion resistance of the sized warp yarn by controlling the starch oxidation technology and adding emulsifiers. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention discloses a starch-based warp sizing solution, with starch as the main component, and designed to incorporate loaded sodium percarbonate, along with ammonium persulfate, O-25, ethylene glycol distearate, and sodium carbonate, so that the sized warp yarn has high abrasion resistance.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The present invention provides a starch-based warp sizing solution, which, by weight, comprises the following raw materials: 30-50 parts starch, 1-1.5 parts supported sodium percarbonate, 0.2-0.5 parts O-25, 0.4-2 parts ethylene glycol distearate, 0.3-0.5 parts sodium carbonate, and 350-500 parts water.

[0008] In some embodiments of the present invention, the starch-based warp sizing solution further includes 0.03-0.6 parts by weight of ammonium persulfate.

[0009] In some embodiments of the present invention, the starch is any one of corn starch, tapioca starch, and potato starch.

[0010] In some embodiments of the present invention, the method for preparing the supported sodium percarbonate includes the following steps: Sodium percarbonate and modified silica gel are mixed, stirred at 40-50℃ for 2-3 hours, and dried to obtain supported sodium percarbonate.

[0011] In some embodiments of the present invention, the mass ratio of sodium percarbonate to modified silica gel is 1:(2.3-3).

[0012] Preferably, the mass ratio of sodium percarbonate to modified silica gel is 1:2.5.

[0013] In some embodiments of the present invention, the method for preparing the modified silicone includes the following steps: (1) Under the condition of pH=2.5-3.5, water glass and sulfuric acid aqueous solution are mixed, stirred for 30-60 min, allowed to stand, filtered, washed, mesoporous silica is added, ball milled, centrifuged, spray dried to obtain product 1 for later use; (2) The product 1 from step (1) was activated at 300-350℃ for 6-7h, cooled and then placed in hydrochloric acid aqueous solution, stirred, washed until neutral, dried, anhydrous toluene and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were added, an inert gas was introduced, and the mixture was refluxed under stirring, cooled and filtered, washed and dried to obtain product 2 for later use. (3) Mix diethylenetriamine and anhydrous methanol, add product 2 from step (2), stir, shake, and dry to obtain modified silica gel.

[0014] In some embodiments of the present invention, in step (1), the mass ratio of sulfuric acid in water glass and sulfuric acid aqueous solution is (4.5-5.5):1.

[0015] In some embodiments of the present invention, in step (2), the mass ratio of product 1 to N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is 1:(0.08-0.12).

[0016] In some embodiments of the present invention, the mass ratio of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane to diethylenetriamine is 1:(4.5-5.5).

[0017] Adding a certain amount of sodium percarbonate as an oxidant to the warp sizing solution can improve the starch oxidation activity, thereby enhancing the film-forming toughness and interfacial adhesion strength of the sizing solution. This effectively improves the abrasion resistance of the warp yarn and reduces the sizing rate, thus lowering production costs. However, sodium percarbonate suffers from poor high-temperature stability and its oxidation effect as a standalone oxidant is not ideal. The porous structure of silica gel can be used as a carrier to load sodium percarbonate and improve its stability. However, the limited number of active sites on the surface of unmodified silica gel results in weak hydrogen bonding with sodium percarbonate, and the loading capacity needs to be improved.

[0018] To address the aforementioned issues, the applicant designed and synthesized a modified silica gel. By loading sodium percarbonate onto the modified silica gel, a supported sodium percarbonate was obtained. First, by controlling the ratio of water glass to sulfuric acid aqueous solution and adding mesoporous silica, a silica gel composite material with high specific surface area and mass transfer channels was synthesized, providing sufficient surface active sites for subsequent modification. Further, the applicant sequentially introduced N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and diethylenetriamine. N-(2-aminoethyl)-3-aminopropyltrimethoxysilane stably grafted the diamino structure onto the silica gel surface through covalent bonding with hydroxyl groups on the silica gel surface, significantly increasing the adsorption sites on the silica gel surface. Diethylenetriamine, on the other hand, adsorbed into the silica gel pore structure through hydrogen bonding and van der Waals forces, increasing the density of amino sites and thus synergistically improving the loading capacity of sodium percarbonate. Even further, the applicant added a certain amount of ammonium persulfate to synergistically act as an oxidant with the supported sodium percarbonate, adding it stepwise during the preparation of the warp sizing solution, thereby enhancing the oxidation intensity in the later stages of preparation and achieving a synergistic effect on starch oxidation.

[0019] In another aspect, the present invention provides a method for preparing a starch-based warp sizing solution, comprising the following steps: Under normal temperature conditions, sodium carbonate, O-25 and ethylene glycol distearate are added to water and stirred. Starch and supported sodium percarbonate are then added, and ammonium persulfate is added while stirring. The temperature is raised to 90-120℃ and stirred for 25-55 minutes to obtain starch-based warp sizing solution.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention discloses a starch-based warp sizing solution, with starch as the main component, and designed to add loaded sodium percarbonate, and combined with ammonium persulfate, O-25, ethylene glycol distearate and sodium carbonate. Through the synergistic effect between the components, the sized warp yarn has high abrasion resistance, and at the same time the sizing rate of the warp yarn can be reduced.

[0021] (2) The present invention designs and synthesizes a modified silica gel. First, by controlling the ratio between water glass and sulfuric acid aqueous solution and adding mesoporous silica, a silica gel composite material with high specific surface area and mass transfer channels is synthesized. Then, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and diethylenetriamine are introduced in sequence to increase the loading of sodium percarbonate. Then, sodium percarbonate is loaded with modified silica gel to obtain supported sodium percarbonate. Finally, a certain amount of ammonium persulfate is used in combination with supported sodium percarbonate as an oxidant and added step by step in the preparation of warp sizing solution to improve the oxidation intensity in the later stage of preparation and play a synergistic effect on the oxidation of starch, thereby improving the abrasion resistance of the sizing warp yarn. Detailed Implementation

[0022] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0023] In the following examples and comparative examples, except for supported sodium percarbonate and modified silica gel, all other compound monomers and related reagents used were commercially available. Corn starch was purchased from Jinan Shenglong Chemical Co., Ltd.; water glass with a modulus of 2.8 was purchased from Wuhan Jiyesheng Chemical Co., Ltd.; and mesoporous silica had a pore size of 7 nm.

[0024] Preparation Example 1 The synthesis method of modified silica gel A includes the following steps: (1) Under pH=3 conditions, 50g of water glass and 100ml of 1mol / L sulfuric acid aqueous solution were mixed, stirred for 45min, allowed to stand for 12h, filtered through a 200nm filter membrane, washed with deionized water until the silica concentration was greater than 99.5%, 25g of mesoporous silica (pore size 7nm) was added, ball milled at 25℃ and 300r / min for 6h, centrifuged, and spray dried (inlet temperature 160℃, outlet temperature 80℃) to obtain product 1 for later use; (2) Place 10g of product 1 from step (1) at 330℃ for 6.5h, cool it and then place it in 100ml of 3mol / L hydrochloric acid aqueous solution, stir for 10h, wash with deionized water until neutral, dry at 60℃ for 10h, add 80ml of anhydrous toluene and 1g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, purge with nitrogen, reflux at 60℃ for 4h under stirring (add 0.5ml of deionized water at the same time), cool and filter, wash with 50ml of anhydrous methanol and 50ml of toluene twice, dry under vacuum at 60℃ for 24h to obtain product 2 for later use; (3) Mix 5g of diethylenetriamine and 125ml of anhydrous methanol, add product 2 from step (2), stir for 2h, shake for 4h, dry at 60℃ for 4h, and vacuum dry at 80℃ for 12h to obtain modified silica gel A.

[0025] Preparation Example 2 Modified silicone B is prepared in the same way as in Preparation Example 1, except that commercially available conventional silicone is used to replace product 1.

[0026] Commercially available standard silicone uses type B silicone.

[0027] Preparation Example 3 Modified silica gel C is prepared in the same way as in preparation example 1, except that the mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in step (2) is replaced with 0.5g.

[0028] Preparation Example 4 Modified silica gel D is prepared in the same way as in preparation example 1, except that the mass of diethylenetriamine in step (3) is replaced with 4g.

[0029] Preparation Example 5 Modified silica gel E is prepared in the same way as in preparation example 1, except that step (3) is omitted, that is, product 2 is directly used as modified silica gel.

[0030] Preparation Example 6 The method for synthesizing modified silica gel F includes the following steps: (1) Same as preparation example 1; (2) Mix 5g of diethylenetriamine and 125ml of anhydrous methanol, add product 1 from step (1), stir for 2h, shake for 4h, dry at 60℃ for 4h, and vacuum dry at 105℃ for 12h to obtain modified silica gel F.

[0031] Preparation Example 7 The method for synthesizing supported sodium percarbonate-1 includes the following steps: 4g of sodium percarbonate and 10g of modified silica gel A were mixed, stirred at 45℃ for 2.5h, and dried at 60℃ for 8h to obtain supported sodium percarbonate-1.

[0032] Preparation Example 8 Supported sodium percarbonate-2 is prepared in the same way as in preparation example 7, except that the mass of modified silica gel A is replaced with 8g.

[0033] Preparation Example 9 Supported sodium percarbonate-3 is prepared in the same way as in preparation example 7, except that the mass of modified silica gel A is replaced with 15g.

[0034] Preparation Example 10 Supported sodium percarbonate-4 is prepared in the same way as in preparation example 7, except that modified silica gel A is replaced by an equal amount of modified silica gel B.

[0035] Preparation Example 11 Supported sodium percarbonate-5 is prepared in the same way as in preparation example 7, except that modified silica gel A is replaced by an equal amount of modified silica gel C.

[0036] Preparation Example 12 Supported sodium percarbonate-6 is prepared in the same way as in preparation example 7, except that modified silica gel A is replaced by an equal amount of modified silica gel D.

[0037] Preparation Example 13 Supported sodium percarbonate-7 is prepared in the same way as in preparation example 7, except that modified silica gel A is replaced by an equal amount of modified silica gel E.

[0038] Preparation Example 14 Supported sodium percarbonate-8 is prepared in the same way as in preparation example 7, except that modified silica gel A is replaced by an equal amount of modified silica gel F.

[0039] Example 1 A starch-based warp sizing solution, by weight, comprises the following raw materials: 40 parts corn starch, 1.2 parts supported sodium percarbonate-1, 0.04 parts ammonium persulfate, 0.32 parts O-25, 1.2 parts ethylene glycol distearate, 0.4 parts sodium carbonate, and 400 parts water.

[0040] The method for preparing starch-based warp sizing in this embodiment includes the following steps: Sodium carbonate, O-25 and ethylene glycol distearate were added to water at 25°C and stirred until homogeneous. Corn starch and supported sodium percarbonate were then added, and ammonium persulfate was added while stirring. The temperature was raised to 95°C and stirred for 50 minutes to obtain starch-based warp sizing solution.

[0041] Example 2 A starch-based warp sizing solution, by weight, comprises the following raw materials: 40 parts corn starch, 1 part supported sodium percarbonate-1, 0.03 parts ammonium persulfate, 0.2 parts O-25, 1 part ethylene glycol distearate, 0.3 parts sodium carbonate, and 400 parts water.

[0042] The method for preparing starch-based warp sizing in this embodiment includes the following steps: At 25°C, sodium carbonate, O-25 and ethylene glycol distearate are added to water and stirred until homogeneous. Corn starch and supported sodium percarbonate-1 are then added, and ammonium persulfate is added while stirring. The temperature is raised to 90°C and stirred for 35 minutes to obtain starch-based warp slurry.

[0043] Example 3 A starch-based warp sizing solution, by weight, comprises the following raw materials: 50 parts corn starch, 1.5 parts supported sodium percarbonate-1, 0.03 parts ammonium persulfate, 0.5 parts O-25, 2 parts ethylene glycol distearate, 0.3 parts sodium carbonate, and 500 parts water.

[0044] The method for preparing starch-based warp sizing in this embodiment includes the following steps: At 25°C, sodium carbonate, O-25 and ethylene glycol distearate are added to water and stirred until homogeneous. Corn starch and supported sodium percarbonate-1 are then added, and ammonium persulfate is added while stirring. The temperature is raised to 100°C and stirred for 25 minutes to obtain starch-based warp sizing solution.

[0045] Example 4 A starch-based warp sizing solution, by weight, comprises the following raw materials: 40 parts corn starch, 1.2 parts supported sodium percarbonate-1, 0.32 parts O-25, 1.6 parts ethylene glycol distearate, 0.4 parts sodium carbonate, and 400 parts water.

[0046] The method for preparing starch-based warp sizing in this embodiment includes the following steps: At 25°C, sodium carbonate, O-25 and ethylene glycol distearate are added to water and stirred until homogeneous. Then, corn starch and supported sodium percarbonate-1 are added and stirred for 15 minutes. The temperature is then raised to 95°C and stirred for 50 minutes to obtain starch-based warp slurry.

[0047] Example 5 This embodiment provides a starch-based warp slurry and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-2.

[0048] Example 6 This embodiment provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-3.

[0049] Example 7 This embodiment provides a starch-based warp slurry and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-4.

[0050] Example 8 This embodiment provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-5.

[0051] Example 9 This embodiment provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-6.

[0052] Example 10 This embodiment provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-7.

[0053] Example 11 This embodiment provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that supported sodium percarbonate-1 is replaced by an equal amount of supported sodium percarbonate-8.

[0054] Comparative Example 1 This comparative example provides a starch-based warp sizing solution and its preparation method. The specific implementation method is the same as in Example 1, except that sodium percarbonate is used to replace the supported sodium percarbonate-1 in an equal amount.

[0055] Performance testing The relevant properties of the starch-based warp sizing solutions of Examples 1-11 and Comparative Example 1 were tested, and the test results are shown in Table 1.

[0056] On a GA391B sizing machine, the sizing solutions obtained in Examples 1-11 and Comparative Example 1 were used to sizing pure cotton warp yarn (pure cotton fine shuttle 40 count). The sizing speed was 4 m / min, and the sizing rate was controlled at the same 14%. After the sizing was balanced for 24 hours, its performance was tested under standard temperature and humidity conditions, with a temperature of (20±2)℃ and a humidity of (65±2)%.

[0057] Abrasion resistance: Utilizes DHJSD The abrasion resistance of the yarn was measured using a Type 1 sizing abrasion tester. The number of cycles of friction when the yarn broke was recorded. The more cycles, the better the abrasion resistance. The test conditions were: reciprocating speed 60 times / min, temperature 25℃, relative humidity 78%, and weight reading 70.

[0058] Table 1 As shown in Table 1, the sized warp yarns in Examples 1-3 of this invention all exhibit high abrasion resistance. Specifically, Example 4, which did not add ammonium persulfate, resulted in the disappearance of the synergistic oxidation effect between the supported sodium percarbonate and ammonium persulfate, leading to a decrease in the oxidation effect on starch and consequently a significant decrease in the abrasion resistance of the warp yarns. Examples 5-6 involved altering the loading ratio of modified silica gel A to sodium percarbonate during the preparation of the supported sodium percarbonate, while Examples 7-11 involved changing the key components in the synthesis of modified silica gel, reducing the stability and oxidizing properties of the supported sodium percarbonate, all of which resulted in varying degrees of deterioration in the abrasion resistance of the warp yarns. Comparative Example 1, which used an equal amount of sodium percarbonate to replace the supported sodium percarbonate-1, showed even worse abrasion resistance in the warp yarns.

[0059] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A starch-based warp sizing solution, characterized in that, By weight, the starch-based warp sizing solution comprises the following raw materials: 30-50 parts starch, 1-1.5 parts supported sodium percarbonate, 0.2-0.5 parts O-25, 0.4-2 parts ethylene glycol distearate, 0.3-0.5 parts sodium carbonate, and 350-500 parts water.

2. The starch-based warp sizing solution according to claim 1, characterized in that, The starch-based warp sizing solution also includes 0.03-0.6 parts by weight of ammonium persulfate.

3. The starch-based warp sizing solution according to claim 1, characterized in that, The starch is any one of corn starch, tapioca starch, or potato starch.

4. The starch-based warp sizing solution according to claim 1, characterized in that, The method for preparing the supported sodium percarbonate includes the following steps: Sodium percarbonate and modified silica gel are mixed, stirred at 40-50℃ for 2-3 hours, and dried to obtain supported sodium percarbonate.

5. The starch-based warp sizing solution according to claim 4, characterized in that, The mass ratio of sodium percarbonate to modified silica gel is 1:(2.3-3).

6. The starch-based warp sizing solution according to claim 4, characterized in that, The method for preparing the modified silicone includes the following steps: (1) Under the condition of pH=2.5-3.5, water glass and sulfuric acid aqueous solution are mixed, stirred for 30-60 min, allowed to stand, filtered, washed, mesoporous silica is added, ball milled, centrifuged, spray dried to obtain product 1 for later use; (2) The product 1 from step (1) was activated at 300-350℃ for 6-7h, cooled and then placed in hydrochloric acid aqueous solution, stirred, washed until neutral, dried, anhydrous toluene and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were added, an inert gas was introduced, and the mixture was refluxed under stirring, cooled and filtered, washed and dried to obtain product 2 for later use. (3) Mix diethylenetriamine and anhydrous methanol, add product 2 from step (2), stir, shake, and dry to obtain modified silica gel.

7. The starch-based warp sizing solution according to claim 6, characterized in that, In step (1), the mass ratio of sulfuric acid in water glass and sulfuric acid aqueous solution is (4.5-5.5):

1.

8. The starch-based warp sizing solution according to claim 6, characterized in that, In step (2), the mass ratio of product 1 to N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is 1:(0.08-0.12).

9. The starch-based warp sizing solution according to claim 6, characterized in that, The mass ratio of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane to diethylenetriamine is 1:(4.5-5.5).

10. A method for preparing a starch-based warp sizing solution according to any one of claims 2-9, characterized in that, Includes the following steps: Under normal temperature conditions, sodium carbonate, O-25 and ethylene glycol distearate are added to water and stirred. Starch and supported sodium percarbonate are then added, and ammonium persulfate is added while stirring. The temperature is raised to 90-120℃ and stirred for 25-55 minutes to obtain starch-based warp sizing solution.

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