Environment-friendly sizing agent and application thereof in continuous spunbonded filament oil

Abstract

The application discloses an environment-friendly sizing agent and application thereof in a continuous-spun viscose filament oil agent. A novel environment-friendly sizing agent is prepared by emulsion polymerization of N-vinyl pyrrolidone (NVP) and acrylic monomers, so that the continuous-spun viscose filament oil agent containing the sizing agent can endow the viscose fiber with the advantages of low moisture absorption, reduced moisture absorption and re-sticking phenomenon, good film-forming property, flexible film, better cohesion, biodegradability and the like. The application mainly solves the problem of difficult biodegradation of the widely used PVA sizing agent in the prior art of the continuous-spun viscose filament oil agent, and has a very wide development prospect.

Description

Technical Field

[0001] This invention relates to the field of chemical auxiliaries, and more particularly to an environmentally friendly sizing agent and its application in continuous spinning viscose filament oiling agents. Background Technology

[0002] Currently, continuous spinning viscose filament oils and textile sizing agents are widely used in fiber production and processing. Their main function is to impart specific properties to fibers, such as smoothness, softness, cohesion, and antistatic properties, while also improving the stability of fibers during production and use.

[0003] Textile sizing agents mainly consist of film-forming main sizing agents such as starch, polyvinyl alcohol (PVA), and acrylics, along with some sizing auxiliaries. Natural native starch comes from plants and is a renewable resource. Starch is also easily biodegradable. However, native starch has drawbacks such as easy skinning, poor abrasion resistance, rough and brittle sizing films, resulting in unsatisfactory sizing performance. Generally, starch used for sizing undergoes modification treatment. Modified starch sizing agents used in textile sizing are mainly produced through chemical modification methods, and the modifying agents used may contain harmful substances. Sizing agents synthesized using acrylate monomers are the most important type of acrylic sizing agent. This is mainly because they have excellent adhesion to hydrophobic synthetic fibers. Their sizing films are more flexible than PVA, with lower strength, but higher deformability. The problem of excessive viscosity due to moisture absorption, leading to sticking to rollers, needs to be addressed. PVA sizing agents, due to their good film-forming properties, high strength, and good abrasion resistance, have been widely used in the field of continuous spinning viscose fiber auxiliaries in recent years. However, PVA sizing agents have regular and extremely stable molecules that are difficult to biodegrade. As a result, they are subject to environmental barriers imposed by Western countries in the textile export trade. Therefore, there is an urgent need to develop environmentally friendly sizing agents to replace PVA. Summary of the Invention

[0004] To address the aforementioned technical problems, the purpose of this invention is to provide an environmentally friendly sizing agent for continuous spinning viscose filaments and its application.

[0005] The technical solution adopted in this invention is as follows: An environmentally friendly slurry, comprising the following raw materials by weight:

[0006]

[0007] Furthermore, the emulsifier is selected from one or a combination of two or more of octylphenol polyoxyethylene ether-10, sodium dodecyl sulfate, and sodium dodecyl sulfonate.

[0008] Furthermore, the initiator is selected from one or a combination of two or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0009] Furthermore, the acrylic monomer is selected from one or a combination of two or more of hydroxyethyl acrylate, ethyl acrylate, methyl methacrylate and lauryl acrylate.

[0010] This invention provides the application of an environmentally friendly sizing agent in continuous spinning viscose filament oiling.

[0011] A continuous spinning viscose filament oiling agent, containing the above-mentioned environmentally friendly sizing agent, comprises the following raw materials by weight:

[0012]

[0013] Furthermore, the antioxidant is selected from one or more of dilauryl thiodipropionate, distearate thiodipropionate, and 4,4-methylenebis(2,6-di-tert-butylphenol).

[0014] Furthermore, the preservative is selected from one or a combination of two or more of sodium benzoate, potassium sorbate, methylparaben, and butylparaben.

[0015] Furthermore, the antibacterial agent is selected from one or a combination of two or more of isothiazolinone, glutaraldehyde, and sodium pyridine sulfate.

[0016] Furthermore, the coalescence aid is selected from one or a combination of two or more of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, propylene glycol methyl ether acetate, and styrene-acrylic emulsion.

[0017] A method for preparing a continuous spinning viscose filament oiling agent includes the following steps:

[0018] 1) Preparation of pre-emulsion: Mix part of emulsifier, part of initiator and part of deionized water, stir thoroughly, dissolve and then add N-vinylpyrrolidone and acrylic monomer in sequence, continue stirring until uniform to obtain pre-emulsion;

[0019] 2) Preparation of environmentally friendly slurry: Dissolve the remaining emulsifier, sodium bicarbonate and deionized water in an oil bath at 50-55℃, then add part of the pre-emulsion obtained in step 1), continue stirring and add the remaining initiator; then raise the temperature to 70-75℃, and slowly add the remaining pre-emulsion dropwise, completing the addition within 2-3 hours. After keeping the temperature at 70-75℃ for 3-4 hours, adjust the pH of the system to neutral to obtain the environmentally friendly slurry;

[0020] 3) Add antioxidant, preservative, antibacterial agent and coalescing agent to the environmentally friendly sizing agent obtained in step 2) in sequence, stir evenly, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

[0021] The beneficial effects of this invention are:

[0022] 1. This invention prepares a novel environmentally friendly sizing agent by emulsion polymerization of N-vinylpyrrolidone (NVP) and acrylic monomers, which enables the continuous spinning viscose filament oil containing this sizing agent to impart low moisture absorption to viscose fibers and reduce the phenomenon of sticking to rollers due to moisture absorption.

[0023] 2. This invention prepares a novel environmentally friendly sizing agent by emulsion polymerization of N-vinylpyrrolidone (NVP) and acrylic monomers. This sizing agent enables continuous spinning viscose filament oiling agents containing this sizing agent to impart advantages to viscose fibers such as good film-forming properties, film flexibility, good cohesion, and biodegradability.

[0024] 3. This invention prepares a novel environmentally friendly sizing agent by emulsion polymerization of N-vinylpyrrolidone (NVP) and acrylic monomers. This sizing agent solves the problem of the poor biodegradability of PVA sizing agents widely used in the existing technology of continuous spinning viscose filament oiling agents, and has a very broad development prospect. Detailed Implementation

[0025] The content and technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0026] Example 1: An environmentally friendly sizing agent and a continuous spinning viscose filament oil (I) An environmentally friendly sizing agent, composed of the following parts by weight:

[0027]

[0028] (II) Oiling agent for continuous spinning viscose filaments, with the following composition by weight:

[0029]

[0030] (III) Oiling agent for continuous spinning viscose filament, the preparation method is as follows:

[0031] 1. Preparation of pre-emulsion:

[0032] Mix 0.26 parts of octylphenol polyoxyethylene ether-10, 0.52 parts of sodium dodecyl sulfonate, 0.2 parts of ammonium persulfate and 30 parts of deionized water, stir thoroughly and dissolve, then add 36 parts of N-vinylpyrrolidone and 24 parts of lauryl acrylate in sequence, and continue stirring thoroughly to obtain a pre-emulsion.

[0033] 2. Preparation of environmentally friendly slurry:

[0034] Dissolve 0.14 parts of octylphenol polyoxyethylene ether-10, 0.28 parts of sodium dodecyl sulfonate, 0.2 parts of sodium bicarbonate, and 55 parts of deionized water in an oil bath at 50°C. Add about 5 parts of the pre-emulsion obtained in step 1, continue stirring, and then add 0.1 parts of ammonium persulfate dissolved in 5 parts of water. Then raise the temperature to 70°C and slowly add the remaining pre-emulsion dropwise over 2 hours. After maintaining the temperature at 70°C for 4 hours, adjust the pH to neutral with ammonia water to obtain an environmentally friendly slurry.

[0035] 3. Preparation of oiling agent for continuous spinning viscose filament

[0036] Take 50 parts of the environmentally friendly sizing agent obtained in step 2, and add 0.5 parts of dilauryl thiodipropionate, 0.5 parts of potassium sorbate, 0.5 parts of glutaraldehyde and 0.6 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate in sequence. Stir evenly, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

[0037] Example 2: An environmentally friendly sizing agent and a continuous spinning viscose filament oil (I) An environmentally friendly sizing agent, composed of the following parts by weight:

[0038]

[0039] (II) Oiling agent for continuous spinning viscose filaments, with the following composition by weight:

[0040]

[0041] (III) Oiling agent for continuous spinning viscose filament, the preparation method is as follows:

[0042] 1. Preparation of pre-emulsion:

[0043] Mix 0.265 parts of octylphenol polyoxyethylene ether-10, 0.528 parts of sodium dodecyl sulfate, 0.2 parts of potassium persulfate, and 30 parts of deionized water, stir thoroughly, and after dissolving, add 32.5 parts of N-vinylpyrrolidone and 28.5 parts of ethyl acrylate in sequence, and continue stirring thoroughly to obtain a pre-emulsion.

[0044] 2. Preparation of environmentally friendly slurry:

[0045] Dissolve 0.142 parts of octylphenol polyoxyethylene ether-10, 0.285 parts of sodium dodecyl sulfate, 54 parts of deionized water, and 0.3 parts of sodium bicarbonate in an oil bath at 50°C. Add about 5 parts of the pre-emulsion obtained in step 1, continue stirring, and then add 0.105 parts of potassium persulfate dissolved in 5 parts of water. Then raise the temperature to 70°C and slowly add the remaining pre-emulsion dropwise over 2 hours. After maintaining the temperature at 70°C for 3 hours, adjust the pH to neutral with ammonia water to obtain an environmentally friendly slurry.

[0046] 3. Preparation of oiling agent for continuous spinning viscose filament

[0047] Take 60 parts of the environmentally friendly sizing agent obtained in step 2, add 0.5 parts of 4,4-methylenebis(2,6-di-tert-butylphenol), 0.5 parts of sodium benzoate, 0.5 parts of isothiazolinone and 0.5 parts of propylene glycol methyl ether acetate, stir evenly, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

[0048] Example 3: An environmentally friendly sizing agent and continuous spun viscose filament oil

[0049] (a) An environmentally friendly slurry, comprising the following components by weight:

[0050]

[0051] (ii) Oiling agent for continuous spinning viscose filament, with the following composition by weight:

[0052]

[0053] (III) Oiling agent for continuous spinning viscose filament, the preparation method is as follows:

[0054] 1. Preparation of pre-emulsion:

[0055] Mix 0.306 parts of octylphenol polyoxyethylene ether-10, 0.605 parts of sodium dodecyl sulfonate, 0.23 parts of sodium persulfate, and 35 parts of deionized water, stir thoroughly, and after dissolving, add 35 parts of N-vinylpyrrolidone and 34 parts of methyl methacrylate in sequence, and continue stirring thoroughly to obtain a pre-emulsion.

[0056] 2. Preparation of environmentally friendly slurry:

[0057] Dissolve 0.164 parts of octylphenol polyoxyethylene ether-10, 0.325 parts of sodium dodecyl sulfonate, 0.2 parts of sodium bicarbonate, and 40 parts of deionized water in a 50°C oil bath. Add about 5 parts of the pre-emulsion obtained in step 1, continue stirring, and then add 0.12 parts of sodium persulfate dissolved in 5 parts of water. Then raise the temperature to 75°C and slowly add the remaining pre-emulsion dropwise over 2 hours. After maintaining the temperature at 75°C for 4 hours, adjust the pH to neutral with ammonia water to obtain an environmentally friendly slurry.

[0058] 3. Preparation of oiling agent for continuous spinning viscose filament

[0059] Take 60 parts of the environmentally friendly sizing agent obtained in step 2, and add 0.5 parts of distearate thiodipropionate, 0.5 parts of butyl p-hydroxybenzoate, 0.5 parts of sodium pyridine sulfate and 0.5 parts of styrene-acrylic emulsion in sequence. Stir evenly, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

[0060] Example 4: An environmentally friendly sizing agent and a continuous spinning viscose filament oil (I) An environmentally friendly sizing agent, composed of the following parts by weight:

[0061]

[0062] (II) Oiling agent for continuous spinning viscose filaments, with the following composition by weight:

[0063]

[0064] (III) Oiling agent for continuous spinning viscose filament, the preparation method is as follows:

[0065] 1. Preparation of pre-emulsion:

[0066] Mix 0.286 parts of octylphenol polyoxyethylene ether-10, 0.572 parts of sodium dodecyl sulfate, 0.22 parts of ammonium persulfate, and 35 parts of deionized water, stir thoroughly, and after dissolving, add 34 parts of N-vinylpyrrolidone, 7 parts of hydroxyethyl acrylate, and 25 parts of ethyl acrylate in sequence, and continue stirring thoroughly to obtain a pre-emulsion.

[0067] 2. Preparation of environmentally friendly slurry:

[0068] Dissolve 0.154 parts of octylphenol polyoxyethylene ether-10, 0.308 parts of sodium dodecyl sulfate, 0.3 parts of sodium bicarbonate, and 44 parts of deionized water in an oil bath at 55°C. Add about 5 parts of the pre-emulsion obtained in step 1, continue stirring, and then add 0.11 parts of ammonium persulfate dissolved in 5 parts of water. Then raise the temperature to 75°C and slowly add the remaining pre-emulsion dropwise over 2 hours. After maintaining the temperature at 75°C for 4 hours, adjust the pH to neutral with ammonia water to obtain an environmentally friendly slurry.

[0069] 3. Preparation of oiling agent for continuous spinning viscose filament

[0070] Take 50 parts of the environmentally friendly sizing agent obtained in step 2, and add 0.5 parts of 4,4-methylenebis(2,6-di-tert-butylphenol), 0.5 parts of methylparaben, 0.5 parts of glutaraldehyde, and 1 part of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate in sequence. Stir well, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

[0071] Comparative Example 1

[0072] By replacing the environmentally friendly sizing agent in Example 1 with a PVA sizing agent, and keeping everything else the same as in Example 1, a continuous spun viscose filament oil containing a PVA sizing agent is obtained.

[0073] Stability Test: The oils prepared in Examples 1-4 and Comparative Example 1 were dissolved in deionized water to prepare working solutions with a concentration of 50 g / L. These solutions were then used for spinning on a continuous viscose filament production line, and the fiber performance was tested. The stability of the oils was tested using low-temperature and high-temperature storage. 100 ml samples were placed in a refrigerator at (-3 to -10)℃ for 24 hours, and then observed for crystallization or precipitation upon returning to room temperature. Alternatively, 100 ml samples were placed in an insulated box at (40±1)℃ for 24 hours, and then immediately observed for stratification or turbidity. The test results are shown in Table 1.

[0074] Cohesion test: The oils prepared in Examples 1-4 and Comparative Example 1 were dissolved in deionized water to prepare working solutions with a concentration of 50 g / L. These solutions were then applied to viscose filaments during continuous spinning and the fibers were tested for performance. A cohesion tester was used to test the fibers treated with different oils. Viscose filaments were wound back and forth on hooks from left to right, with nine hooks on the left and ten on the right. Finally, the viscose filaments were pressed tightly under the knurled nut, resulting in a total of 20 filaments. To ensure appropriate tension on the viscose filaments, a certain weight was hung inside the ring at the end of the chain. The area under the knurled nut was the friction zone, where the viscose filaments could bend under tension. During reciprocating motion, the sample filaments underwent bending friction between the alternating friction plates. The test was terminated when more than half (10 filaments) of the sample filaments had a 6 mm long crack, and the number of friction cycles was recorded. The test results are shown in Table 1.

[0075] Water absorption test: Solid slurry films were obtained by drying the samples from Examples 1-4 and Comparative Example 1. The water absorption rate was used to test the moisture absorption and sticking of the solid slurry to the rollers. Approximately 1g of slurry film was weighed and placed in an oven at 105℃ to dry to constant weight. The samples were then placed at 20℃ and 70% relative humidity for 240h, and weighed. The water absorption test results were calculated and are shown in Table 1.

[0076] Biodegradability testing: Currently, the biodegradability of slurry wastewater is generally evaluated through BOD5 and COD. Cr The ratio of BOD5 to COD is used to determine this. Cr The higher the value, the better the biodegradability.

[0077] COD value determination: Take 10 mg of the oil prepared in Examples 1-4 and Comparative Example 1, dilute with deionized water to 20 ml, place 20 ml of the sample in a 250 ml ground glass reflux flask, accurately add 10 ml of potassium dichromate standard solution and several small glass beads. Slowly add 30 ml of sulfuric acid-silver sulfate solution, gently shake the conical flask to mix the solution, connect the ground glass reflux condenser, and heat under reflux for two hours. After cooling, rinse the condenser wall with 90 ml of distilled water, cool again, add 3 drops of ferroin indicator solution, and titrate with ferrous ammonium sulfate solution. The titration endpoint is reached when the solution color changes from yellow through blue-green to reddish-brown. Record the titration volume. The test results are shown in Table 1.

[0078] Blank test: Perform a blank test using 20.0 ml of water instead of the sample, following the same procedure. All other reagents and samples were measured in the same way. Record the volume of ferrous ammonium sulfate standard solution consumed during the blank titration.

[0079] BOD value determination: The BOD test was performed using the German OxiTop Control instrument. The test steps are as follows: (1) Dilute the oil to be tested to reach the required range. Take a certain volume of the diluted oil and add it to the brown dissolved oxygen bottle; (2) Add 2 drops of 0.5g / L allyl thiourea solution to the dissolved oxygen bottle, put in a stir bar, and inoculate microorganisms. When microorganisms decompose organic matter, they will consume the oxygen in the sealed dissolved oxygen bottle and produce carbon dioxide through respiration; (3) Insert the rubber sleeve, add 2-3 sodium hydroxide pills to the rubber sleeve with tweezers, screw the sensor head into the bottle, and then place the bottle on the stirring base and put it in the incubator for 5 days at a temperature of 20℃±1. Sodium hydroxide absorbs the carbon dioxide produced by microorganisms, which leads to a decrease in the gas pressure inside the bottle. The sensor head senses the pressure change and transmits it to the controller, which converts it into a BOD value. The test results are shown in Table 1.

[0080] Table 1 Performance Indicators of Oils and Fibers

[0081]

[0082] In comparison, the continuous spun viscose filament oiling agent containing environmentally friendly sizing agent of the present invention has good stability and film-forming properties, and has sufficient moisture absorption and is not easy to stick to the roller. The fibers have excellent cohesion and biodegradability, which can meet the needs of production and use.

Claims

1. The application of an environmentally friendly sizing agent in continuous spinning viscose filament oiling, characterized in that, The environmentally friendly slurry, by weight, comprises the following raw materials: Emulsifier 1.2-1.4 parts, Initiator 0.3-0.35 parts, 32-36 parts of N-vinylpyrrolidone 24-34 parts of acrylate monomer Sodium bicarbonate 0.2-0.3 parts, 80-90 parts deionized water.

2. The application of the environmentally friendly sizing agent according to claim 1 in the oiling agent for continuous spinning viscose filaments, characterized in that, The emulsifier is selected from one or a combination of two or more of octylphenol polyoxyethylene ether-10, sodium dodecyl sulfate, and sodium dodecyl sulfonate.

3. The application of the environmentally friendly sizing agent according to claim 1 in the oiling agent for continuous spinning viscose filaments, characterized in that, The initiator is selected from one or a combination of two or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

4. The application of the environmentally friendly sizing agent according to claim 1 in the oiling agent for continuous spinning viscose filaments, characterized in that, The acrylate monomer is selected from one or more of hydroxyethyl acrylate, ethyl acrylate, methyl methacrylate and lauryl acrylate.

5. A continuous spinning viscose filament oiling agent, characterized in that, The continuous spinning viscose filament oiling agent, comprising the environmentally friendly sizing agent described in any one of claims 1-4, in the application of the environmentally friendly sizing agent in continuous spinning viscose filament oiling agent, includes the following raw materials by weight: 40-60 parts of environmentally friendly slurry Antioxidant 0.5-1 part Preservative 0.5-1 part Antibacterial agent 0.5-1 part, 0.5-1 part of agglomeration aid.

6. The continuous spinning viscose filament oiling agent according to claim 5, characterized in that, The antioxidant is selected from one or a combination of two or more of dilauryl thiodipropionate, distearate thiodipropionate, and 4,4-methylenebis(2,6-di-tert-butylphenol).

7. The continuous spinning viscose filament oiling agent according to claim 5, characterized in that, The preservative is selected from one or a combination of two or more of sodium benzoate, potassium sorbate, methylparaben, and butylparaben; the antibacterial agent is selected from one or a combination of two or more of isothiazolinone, glutaraldehyde, and sodium pyridine sulfate.

8. The continuous spinning viscose filament oiling agent according to claim 5, characterized in that, The coalescence aid is selected from one or a combination of two or more of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, propylene glycol methyl ether acetate, and styrene-acrylic emulsion.

9. A method for preparing a continuous spun viscose filament oiling agent according to any one of claims 5-8, characterized in that, The preparation method includes the following steps: 1) Preparation of pre-emulsion: Mix part of emulsifier, part of initiator and part of deionized water, stir thoroughly, dissolve and then add N-vinylpyrrolidone and acrylic monomer in sequence, continue stirring until uniform to obtain pre-emulsion; 2) Preparation of environmentally friendly slurry: Dissolve the remaining emulsifier, sodium bicarbonate and deionized water in an oil bath at 50-55℃, then add part of the pre-emulsion obtained in step 1), continue stirring and add the remaining initiator; then raise the temperature to 70-75℃, and slowly add the remaining pre-emulsion dropwise over 2-3 hours. After maintaining the temperature at 70-75℃ for 3-4 hours, adjust the pH of the system to neutral to obtain the environmentally friendly slurry. 3) Add antioxidant, preservative, antibacterial agent and coalescing agent to the environmentally friendly sizing agent obtained in step 2) in sequence, stir evenly, filter, and obtain a continuous spun viscose filament oil containing the environmentally friendly sizing agent.

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