Vinyl acetate-ethylene copolymer emulsion composition and vinyl acetate-ethylene copolymer emulsion for textiles as well as preparation method and application of vinyl acetate-ethylene copolymer emulsion composition and vinyl acetate-ethylene copolymer emulsion

Abstract

The invention relates to the field of textile compounding, and discloses a vinyl acetate-ethylene copolymer emulsion composition and vinyl acetate-ethylene copolymer emulsion for textiles as well as a preparation method and application of the vinyl acetate-ethylene copolymer emulsion composition and the vinyl acetate-ethylene copolymer emulsion, the composition comprises vinyl acetate, ethylene, protective colloid and water, the protective colloid is polyvinyl alcohol which is equivalent to 100 parts by weight of water, and the protective colloid is polyvinyl alcohol which is equivalent to 100 parts by weight of water. The content of the vinyl acetate is 115-121 parts by weight, the content of the ethylene is 21-27 parts by weight, and the content of the protective colloid is 5.5-6.5 parts by weight. By adopting the specific protective colloid, the vinyl acetate-ethylene copolymer emulsion is further adjusted, the cost is low, the method is simple, and the prepared adhesive film can be soft.

Description

Technical Field

[0001] This invention relates to the field of textile composites, specifically to a vinyl acetate-ethylene copolymer emulsion composition for textiles, a vinyl acetate-ethylene copolymer emulsion, its preparation method, and its application. Background Technology

[0002] In the mid-1960s, vinyl acetate-ethylene copolymer emulsion (hereinafter referred to as VAE emulsion) was first industrialized. Due to its good low-temperature film-forming properties, flexibility and adhesion, VAE emulsion is widely used in construction (including latex powder, waterproof coatings, interior wall coatings), adhesives (including packaging, woodworking, cigarette adhesives), textiles (including material composites, printing, carpets, non-woven fabrics, coatings, etc.) and other fields.

[0003] VAE emulsions are mainly used in textile composites for tufted carpets, needle-punched carpets, woven carpets, artificial fur, electrostatic flocking, decorative fabric coatings, printing pastes, and nonwoven fabric adhesive bases, imparting properties such as abrasion resistance, water resistance, and dyeability to textiles. However, sometimes the dried film of VAE emulsion can reduce the softness of the laminated fabric, affecting its hand feel.

[0004] Existing technologies have conducted extensive research on improving fabric softness:

[0005] CN117211070A discloses a method for synthesizing a cationic acrylate emulsion and its application. The method includes: adding an emulsifier to deionized water, stirring to dissolve, adding acrylate monomers and an initiator, and continuing to stir the reaction to obtain a pre-emulsion; stirring the pre-emulsion, modified polyethyleneimine, and silica sol together, adjusting the pH to 7-8, and then filtering to obtain the desired cationic acrylate emulsion. By adding modified polyethyleneimine to the acrylate emulsion, the resulting emulsion, when used for textile treatment, can further improve the softness, comfort, and wrinkle resistance of textiles while ensuring a deepening effect.

[0006] CN107868198A discloses a water-based polyurethane paste emulsion for textile printing and its preparation method. The raw materials, by weight ratio, consist of isophorone diisocyanate 20-50, isophorone diisocyanate trimer 20-40, polytrimethylene glycol 5-20, polybutylene adipate diol 30-60, polyethylene oxide diol 30-50, 2,2,4-trimethyl-1,3pentanediol 3-5, dimethylolbutyric acid 2-4, triethylamine 1-3, deionized water 210-440, and hydrazine hydrate 4-6. By adding the hydrophilic polyethylene oxide diol, the film surface expands during the film-forming process, achieving a soft and smooth hand feel.

[0007] CN110565377B discloses an organosilicon quaternary ammonium salt for improving the whiteness and softness of fabrics, its preparation method and emulsion, which forms an antibacterial, yellowing-resistant and soft fabric by introducing γ-chloropropyltrimethylsiloxane into the quaternary ammonium compound.

[0008] CN107476063B discloses a water-based acrylic coating adhesive for textiles with good softness, cold resistance, elasticity, fastness, and hydrostatic pressure resistance, and its preparation method. The coating adhesive contains the following raw materials by weight ratio: sodium 1-acryloxy-2-hydroxypropanesulfonate 5.5-6.5, N-hydroxyethylacrylamide 4-4.5, methacrylic acid 2.5-3, hydroxyethyl methacrylate 4.5-5.5, 2-ethylhexyl acrylate 35-39, n-butyl acrylate 133-140, methyl methacrylate 44-47, reactive organosilicon slip modifier 5.5-6, trifluoroethyl acrylate 3-3.5, ammonium persulfate 0.9-1.1, sodium bisulfite 0.1-0.2, and deionized water 262-284. The application of 2-ethylhexyl acrylate improves the cold resistance, softness, and water resistance of the polymer film.

[0009] CN109371687B discloses a highly flexible waterborne polyurethane finishing agent for textiles and its preparation method. The agent is prepared by reacting the following raw materials: polyether diol, aliphatic diisocyanate, nonionic chain extender, ionic hydrophilic chain extender, N-methyl-2-pyrrolidone, isopropanol, linear polyether block amino silicone oil, neutralizing agent, and deionized water. The method prepares a highly flexible waterborne polyurethane finishing agent, resulting in a film with excellent softness properties, which can improve the hand feel of the finished fabric by 1-2 grades.

[0010] However, the above methods all involve adding modified substances to the emulsion to improve the softness of the fabric, thereby increasing the softness of the emulsion film. This approach has the disadvantages of high cost and poor environmental friendliness.

[0011] Therefore, it is of great significance to research and develop a vinyl acetate-ethylene copolymer emulsion for textiles. Summary of the Invention

[0012] The purpose of this invention is to overcome the problem of high cost in the prior art and to provide a vinyl acetate-ethylene copolymer emulsion composition for textiles, a vinyl acetate-ethylene copolymer emulsion, its preparation method and application. This invention uses a specific protective colloid to adjust the vinyl acetate-ethylene copolymer emulsion, which is low in cost, simple in method, and can make the prepared film soft.

[0013] To achieve the above objectives, the first aspect of the present invention provides a vinyl acetate-ethylene copolymer emulsion composition for textiles, wherein the composition comprises vinyl acetate, ethylene, a protective colloid, and water, wherein the protective colloid is polyvinyl alcohol and is equivalent to 100 parts by weight of water, the content of vinyl acetate is 115-121 parts by weight, the content of ethylene is 21-27 parts by weight, and the content of the protective colloid is 5.5-6.5 parts by weight.

[0014] A second aspect of the present invention provides a method for preparing a vinyl acetate-ethylene copolymer emulsion for textiles using the aforementioned composition, wherein the method comprises:

[0015] (1) Mix and stir a portion of vinyl acetate, ethylene, protective colloid and water;

[0016] (2) Add the first part of oxidant and the first part of reducing agent to the product obtained in step (1) to carry out the first reaction;

[0017] (3) Add another part of vinyl acetate, ethylene, a second part of oxidant, and a second part of reducing agent to the product obtained in step (2) to carry out a second reaction;

[0018] (4) Add the remaining oxidant and the remaining reducing agent to the product obtained in step (3) for post-treatment, then add pH adjuster, discharge, and filter to obtain vinyl acetate-ethylene copolymer emulsion for textiles.

[0019] A third aspect of the present invention provides a vinyl acetate-ethylene copolymer emulsion for textiles prepared by the method described above.

[0020] The fourth aspect of the present invention provides an application of the aforementioned vinyl acetate-ethylene copolymer emulsion for textiles as one or more of coatings, slurries and adhesives in textiles.

[0021] Through the above technical solution, the present invention has the following beneficial effects:

[0022] (1) This invention is implemented by adjusting the VAE emulsion formula, only adjusting the type and ratio of the protective colloid, and the method is simple.

[0023] (2) The protective colloid used in this invention is inexpensive, and the production cost of VAE products is low. Detailed Implementation

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] As previously stated, the first aspect of the present invention provides a vinyl acetate-ethylene copolymer emulsion composition for textiles, wherein the composition comprises vinyl acetate, ethylene, a protective colloid, and water, wherein the protective colloid is polyvinyl alcohol and is equivalent to 100 parts by weight of water, the content of vinyl acetate is 115-121 parts by weight, the content of ethylene is 21-27 parts by weight, and the content of the protective colloid is 5.5-6.5 parts by weight.

[0026] According to the present invention, preferably, the content of vinyl acetate is 116-120 parts by weight (equivalent to 100 parts by weight of water), the content of ethylene is 22-26 parts by weight, and the content of the protective colloid is 5.7-6.3 parts by weight; more preferably, the content of vinyl acetate is 117-119 parts by weight (equivalent to 100 parts by weight of water), the content of ethylene is 23-25 ​​parts by weight, and the content of the protective colloid is 5.8-6.1 parts by weight. In the present invention, limiting the content of vinyl acetate, ethylene, protective colloid, and water within the aforementioned ranges can achieve the effect of a soft and strong film; if the ethylene content is too high, the film strength will be insufficient; if the ethylene content is too low, the film will not be soft enough.

[0027] The inventors of this invention discovered that ethylene, as a soft monomer, can lower the glass transition temperature of VAE and improve the softness of the adhesive film. Regarding the strength and softness of textiles, the technical solution of this invention, using a specific protective colloid, allows the adhesive film to have a strength slightly greater than the strength of the textile itself, achieving good adhesion without reducing the softness of the textile.

[0028] According to the present invention, the polyvinyl alcohol comprises partially hydrolyzed polyvinyl alcohol and fully hydrolyzed polyvinyl alcohol; preferably, the weight ratio of the partially hydrolyzed polyvinyl alcohol to the fully hydrolyzed polyvinyl alcohol is 1:(0.2-0.5), more preferably 1:(0.3-0.4). In the present invention, limiting the weight ratio of the partially hydrolyzed polyvinyl alcohol to the fully hydrolyzed polyvinyl alcohol to the aforementioned range is beneficial because fully hydrolyzed polyvinyl alcohol lacks ester active groups, resulting in fewer interaction points with textile materials during VAE emulsion film formation, thus maintaining a softness effect. If the weight ratio of the partially hydrolyzed polyvinyl alcohol to the fully hydrolyzed polyvinyl alcohol is too high, it will reduce the softness of textiles; if the weight ratio is too low, it will result in poor stability of the VAE emulsion.

[0029] According to the present invention, the degree of polymerization of the polyvinyl alcohol is 500-1700, and the degree of hydrolysis is 88-99 mol%. The degree of hydrolysis represents the percentage of hydroxyl groups in the original group in the product obtained after the hydrolysis reaction, and can also be expressed as a degree of hydrolysis of 88-99%. In the present invention, preferred polyvinyl alcohol types include one or more of 0588, 1788 and 1399.

[0030] According to the present invention, the water is preferably deionized water.

[0031] According to the present invention, the composition further includes a reducing agent, an oxidizing agent, and a pH adjuster.

[0032] According to the present invention, the content of the reducing agent is 0.2-0.6 parts by weight, the content of the oxidizing agent is 0.3-0.7 parts by weight, and the content of the pH adjuster is 0.05-0.09 parts by weight, equivalent to 100 parts by weight of water; preferably, the content of the reducing agent is 0.3-0.5 parts by weight, the content of the oxidizing agent is 0.4-0.6 parts by weight, and the content of the pH adjuster is 0.06-0.08 parts by weight, equivalent to 100 parts by weight of water.

[0033] According to the present invention, the reducing agent is selected from one or more of ascorbic acid, isoascorbate, and tartrate; preferably, the reducing agent is selected from one or more of ascorbic acid, zinc isoascorbate, sodium isoascorbate, magnesium isoascorbate, zinc tartrate, sodium tartrate, and magnesium tartrate; more preferably, the reducing agent is selected from one or more of ascorbic acid, sodium isoascorbate, and potassium tartrate; and even more preferably, the reducing agent is ascorbic acid.

[0034] According to the present invention, the oxidant is an organic peroxide and / or an inorganic peroxide, preferably one or more of tert-butyl hydroperoxide, hydrogen peroxide, potassium persulfate and ammonium persulfate, more preferably tert-butyl hydroperoxide.

[0035] According to the present invention, the pH adjuster is selected from one or more of bicarbonate, acetate, phosphate and sodium hydroxide, preferably sodium hydroxide.

[0036] According to the present invention, the composition further includes a bactericide.

[0037] According to the present invention, the bactericide content is 0.5-1.0 parts by weight, equivalent to 100 parts by weight of water.

[0038] According to the present invention, the bactericide is Kathon.

[0039] A second aspect of the present invention provides a method for preparing a vinyl acetate-ethylene copolymer emulsion for textiles using the aforementioned composition, wherein the method comprises:

[0040] (1) Mix and stir a portion of vinyl acetate, ethylene, protective colloid and water;

[0041] (2) Add the first part of oxidant and the first part of reducing agent to the product obtained in step (1) to carry out the first reaction;

[0042] (3) Add another part of vinyl acetate, ethylene, a second part of oxidant, and a second part of reducing agent to the product obtained in step (2) to carry out a second reaction;

[0043] (4) Add the remaining oxidant and the remaining reducing agent to the product obtained in step (3) for post-treatment, then add pH adjuster, discharge, and filter to obtain vinyl acetate-ethylene copolymer emulsion for textiles.

[0044] According to the present invention, the conditions for the first reaction include: a temperature of 50-54°C and a pressure of 3.6-3.9 MPa; preferably, a temperature of 52-53°C and a pressure of 3.7-3.8 MPa.

[0045] According to the present invention, the conditions for the second reaction include: a temperature of 75-85°C and a pressure of 5.2-6.0 MPa; preferably, a temperature of 78-82°C and a pressure of 5.5-5.8 MPa.

[0046] According to the present invention, when the temperature is 75-85°C and the ethylene pressure rises to 5.0-6.0 MPa, another portion of vinyl acetate is added to carry out a second reaction.

[0047] According to the present invention, the post-processing conditions include: a temperature of 70-80°C and a pressure of 1.5-5.5 MPa; preferably, a temperature of 72-76°C and a pressure of 2-3 MPa.

[0048] According to the present invention, the weight ratio of the portion of vinyl acetate to the other portion of vinyl acetate is (0.7-2.3):1, preferably (1.3-1.7):1.

[0049] According to the present invention, the weight ratio of the first part of the oxidant to the second part of the oxidant and the remaining oxidant is 1:(0.9-1.2):(1.9-2.2), preferably 1:(1.0-1.1):(2.0-2.1).

[0050] According to the present invention, the weight ratio of the first reducing agent to the second reducing agent and the remaining reducing agent is 1:(0.9-1.2):(1.9-2.2), preferably 1:(1.0-1.1):(2.0-2.1).

[0051] A third aspect of the present invention provides a vinyl acetate-ethylene copolymer emulsion for textiles prepared by the method described above.

[0052] The fourth aspect of the present invention provides an application of the aforementioned vinyl acetate-ethylene copolymer emulsion for textiles as one or more of coatings, slurries and adhesives in textiles.

[0053] According to the present invention, vinyl acetate-ethylene copolymer emulsion can be applied to tufted carpets, needle-punched carpets, woven carpets, artificial fur, electrostatic flocking, decorative fabric coatings, printing pastes, and nonwoven fabric adhesive base materials to improve the softness of textiles.

[0054] According to a particularly preferred embodiment of the present invention, a method for preparing a vinyl acetate-ethylene copolymer emulsion for textiles provided by the present invention includes:

[0055] A. Raw material preparation

[0056] Preparation of oxidant solution: Add oxidant and water to the oxidant tank and stir to dissolve;

[0057] Preparation of reducing agent solution: Add reducing agent and water to the reducing agent tank and stir to dissolve;

[0058] Preparation of protective colloidal solution: While stirring, add water and protective colloid sequentially to the dissolving tank, heat to 80-95℃ and dissolve for 60-120 minutes, then cool to 30-60℃ for later use;

[0059] Preparation of post-treatment aids: Add oxidant and water to the post-treatment oxidant tank and stir to dissolve; add reducing agent and water to the post-treatment reducing agent tank and stir to dissolve.

[0060] B. Production by feeding materials

[0061] While stirring, add water and a protective colloidal solution, and after stirring evenly, add 47-84 parts of vinyl acetate monomer. Increase the temperature and pressure. When the temperature reaches 50-54℃ and the pressure reaches 3.6-3.9 MPa, simultaneously add 0.1-0.23 parts of oxidant and 0.07-0.2 parts of reducing agent. When the temperature reaches 75-85℃ and the ethylene pressure rises to 5.2-6.0 MPa, add 31-74 parts of vinyl acetate monomer over 60-150 minutes, continuously adding 0.11-0.25 parts of oxidant and 0.08-0.22 parts of reducing agent. After monomer addition is complete, enter the finishing stage. After degassing, continuously add 0.09-0.22 parts of oxidant and 0.05-0.18 parts of reducing agent over 60 minutes. Then, cool down and add pH adjuster and bactericide, then discharge, filter, and package.

[0062] The composition of various raw materials in this invention is as follows (by weight fraction):

[0063] Vinyl acetate: 115-121 parts;

[0064] Ethylene: 21-27 parts;

[0065] Protective colloid: 5.5-6.5 parts;

[0066] Reducing agent: 0.2-0.6 parts;

[0067] Oxidizing agent: 0.3-0.7 parts;

[0068] pH adjuster: 0.05-0.09 parts;

[0069] Water: 100 portions.

[0070] The present invention will be described in detail below through embodiments.

[0071] In the following examples and comparative examples:

[0072] The fabric softness was evaluated using a self-developed fabric softness testing method. Specifically, the fabric softness test included:

[0073] The VAE emulsion was laminated with the textile, with a dry coating amount of 25 g / m². 2 After drying in a forced-air drying oven at 80℃-90℃ for 10 minutes, remove and cool before evaluating the feel. Softness is graded into 6 levels: 1 for very soft, 2 for soft, 3 for relatively soft, 4 for relatively firm, 5 for firm, and 6 for very firm.

[0074] In this invention, it should be noted that both "parts" and "number of parts" refer to "parts by weight".

[0075] Example 1

[0076] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0077] (1) While stirring, add 100 parts of deionized water, 2.5 parts of PVA1788, 2.0 parts of PVA0588 and 1.5 parts of PVA1399 to the reactor, stir evenly and then add 66 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0078] (2) When the temperature rises to 52℃ and the pressure reaches 3.7MPa, add 0.1 parts of tert-butyl hydrogen peroxide and 0.08 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 78℃ and the ethylene pressure rises to 5.0MPa, add the remaining 51 parts of vinyl acetate monomer, 0.1 parts of continuous tert-butyl hydrogen peroxide, and 0.09 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 72℃ and the pressure reaches 2.0MPa, and the finishing period begins.

[0079] (3) After degassing to the degassing tank, add 0.2 parts of tert-butyl hydrogen peroxide and 0.13 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.06 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0080] Example 2

[0081] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0082] (1) While stirring, add 100 parts of deionized water, 2.5 parts of PVA1788, 2.2 parts of PVA0588 and 1.4 parts of PVA1399 to the reactor, stir evenly and then add 75 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0083] (2) When the temperature rises to 53℃ and the pressure reaches 3.8MPa, add 0.12 parts of tert-butyl hydrogen peroxide and 0.1 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 80℃ and the ethylene pressure rises to 5.0MPa, add the remaining 44 parts of vinyl acetate monomer, 0.13 parts of continuous tert-butyl hydrogen peroxide, and 0.11 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 74℃ and the pressure reaches 2.5MPa, and the finishing period begins.

[0084] (3) After degassing to the degassing tank, add 0.25 parts of tert-butyl hydrogen peroxide and 0.19 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.07 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0085] Example 3

[0086] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0087] (1) While stirring, add 100 parts of deionized water, 2.1 parts of PVA1788, 2.1 parts of PVA0588 and 1.6 parts of PVA1399 to the reactor, stir evenly and then add 70 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0088] (2) When the temperature rises to 53℃ and the pressure reaches 3.9MPa, add 0.13 parts of tert-butyl hydrogen peroxide and 0.12 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 82℃ and the ethylene pressure rises to 5.0MPa, add the remaining 48 parts of vinyl acetate monomer, 0.15 parts of continuous tert-butyl hydrogen peroxide, and 0.13 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 76℃ and the pressure reaches 3.0MPa, and the finishing period begins.

[0089] (3) After degassing to the degassing tank, add 0.32 parts of tert-butyl hydrogen peroxide and 0.25 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.08 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0090] Example 4

[0091] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0092] (1) While stirring, add 100 parts of deionized water, 2.5 parts of PVA1788, 2.2 parts of PVA0588 and 1.0 parts of PVA1399 to the reactor, stir evenly and then add 48 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0093] (2) When the temperature rises to 51℃ and the pressure reaches 3.6MPa, add 0.10 parts of tert-butyl hydrogen peroxide and 0.053 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 75℃ and the ethylene pressure rises to 5.2MPa, add the remaining 68 parts of vinyl acetate monomer, 0.09 parts of continuous tert-butyl hydrogen peroxide, and 0.047 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 70℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0094] (3) After degassing to the degassing tank, add 0.11 parts of tert-butyl hydrogen peroxide and 0.10 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.05 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0095] Example 5

[0096] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0097] (1) While stirring, add 100 parts of deionized water, 2.1 parts of PVA1788, 2.1 parts of PVA0588 and 2.1 parts of PVA1399 to the reactor, stir evenly, add 84 parts of vinyl acetate monomer, and then heat and pressurize.

[0098] (2) When the temperature rises to 54℃ and the pressure reaches 3.9MPa, add 0.16 parts of tert-butyl hydrogen peroxide and 0.136 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 6.0MPa, add the remaining 36 parts of vinyl acetate monomer, 0.19 parts of continuous tert-butyl hydrogen peroxide, and 0.164 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 80℃ and the pressure reaches 5.5MPa, and the finishing period begins.

[0099] (3) After degassing to the degassing tank, add 0.35 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.09 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0100] Example 6

[0101] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0102] (1) While stirring, add 100 parts of deionized water, 2.3 parts of PVA1788, 2.2 parts of PVA0588 and 1.0 parts of PVA1399 to the reactor, stir evenly and then add 55 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0103] (2) When the temperature rises to 50℃ and the pressure reaches 3.9MPa, add 0.19 parts of tert-butyl hydrogen peroxide and 0.045 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 75℃ and the ethylene pressure rises to 6.0MPa, add the remaining 60 parts of vinyl acetate monomer, 0.17 parts of continuous tert-butyl hydrogen peroxide, and 0.06 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 74℃ and the pressure reaches 4.5MPa, and the finishing period begins.

[0104] (3) After degassing, 0.34 parts of tert-butyl hydrogen peroxide and 0.095 parts of ascorbic acid are added for post-treatment; after cooling after post-treatment, 0.09 parts of pH adjuster, bactericide, etc. are added, and the product is discharged, filtered, and packaged; vinyl acetate-ethylene copolymer emulsion is prepared.

[0105] Example 7

[0106] This embodiment illustrates the vinyl acetate-ethylene copolymer emulsion prepared using the method of the present invention.

[0107] (1) While stirring, add 100 parts of deionized water, 2.3 parts of PVA1788, 2.0 parts of PVA0588 and 2.2 parts of PVA1399 to the reactor, stir evenly and then add 82 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0108] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.16 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 5.2MPa, add the remaining 39 parts of vinyl acetate monomer, 0.08 parts of continuous tert-butyl hydrogen peroxide, and 0.14 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 78℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0109] (3) After degassing to the degassing tank, add 0.14 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.05 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare vinyl acetate-ethylene copolymer emulsion.

[0110] Comparative Example 1

[0111] (1) While stirring, add 100 parts of deionized water, 2.8 parts of PVA1788, 2.5 parts of PVA0588 and 2.2 parts of PVA1399 to the reactor, stir evenly and then add 87 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0112] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.16 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 4.0MPa, add the remaining 45 parts of vinyl acetate monomer, 0.08 parts of continuous tert-butyl hydrogen peroxide, and 0.14 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 78℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0113] (3) After degassing, 0.14 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid are added for post-treatment; after cooling after post-treatment, 0.05 parts of pH adjuster and bactericide are added, and the product is discharged, filtered and packaged to obtain a copolymer emulsion.

[0114] Comparative Example 2

[0115] (1) While stirring, add 100 parts of deionized water, 2.6 parts of PVA1788, 2.8 parts of PVA0588 and 2.2 parts of PVA1399 to the reactor, stir evenly and then add 90 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0116] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.16 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 4.5MPa, add the remaining 43 parts of vinyl acetate monomer, 0.08 parts of continuous tert-butyl hydrogen peroxide, and 0.14 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 78℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0117] (3) After degassing, 0.14 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid are added for post-treatment; after cooling after post-treatment, 0.05 parts of pH adjuster and bactericide are added, and the product is discharged, filtered and packaged to obtain a copolymer emulsion.

[0118] Comparative Example 3

[0119] (1) While stirring, add 100 parts of deionized water, 3.0 parts of PVA1788, 2.3 parts of PVA0588 and 2.2 parts of PVA1399 to the reactor, stir evenly and then add 85 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0120] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.16 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 4.3MPa, add the remaining 48 parts of vinyl acetate monomer, 0.08 parts of continuous tert-butyl hydrogen peroxide, and 0.14 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 78℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0121] (3) After degassing, 0.14 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid are added for post-treatment; after cooling after post-treatment, 0.05 parts of pH adjuster and bactericide are added, and the product is discharged, filtered and packaged to obtain a copolymer emulsion.

[0122] Comparative Example 4

[0123] (1) While stirring, add 100 parts of deionized water, 3.0 parts of PVA1788, 2.7 parts of PVA0588 and 0.8 parts of PVA1399 to the reactor, stir evenly and then add 82 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0124] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.16 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 5.2MPa, add the remaining 39 parts of vinyl acetate monomer, 0.08 parts of continuous tert-butyl hydrogen peroxide, and 0.14 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 78℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0125] (3) After degassing, 0.14 parts of tert-butyl hydrogen peroxide and 0.30 parts of ascorbic acid are added for post-treatment; after cooling after post-treatment, 0.05 parts of pH adjuster and bactericide are added, and the product is discharged, filtered and packaged to obtain a copolymer emulsion.

[0126] Test case

[0127] The VAE emulsions prepared using the methods of Examples 1-7 and Comparative Examples 1-4 were used to evaluate the fabric softness, as shown in Table 1.

[0128] Table 1

[0129]

[0130]

[0131] As can be seen from the results in Table 1, the softness of the emulsion prepared according to the present invention was evaluated using the self-developed fabric softness testing method. The softness of Examples 1-7 of the present invention was improved by 1-4 grades compared with Comparative Examples 1-4; this proves that the method used in the present invention can improve the softness of VAE composite textile materials with low production cost and simple method.

[0132] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A vinyl acetate-ethylene copolymer emulsion composition for textiles, characterized in that, The composition comprises vinyl acetate, ethylene, a protective colloid, and water, wherein the protective colloid is polyvinyl alcohol and is equivalent to 100 parts by weight of water, the content of vinyl acetate is 115-121 parts by weight, the content of ethylene is 21-27 parts by weight, and the content of the protective colloid is 5.5-6.5 parts by weight.

2. The composition according to claim 1, comprising 100 parts by weight of water, wherein the content of vinyl acetate is 116-120 parts by weight, the content of ethylene is 22-26 parts by weight, and the content of the protective colloid is 5.7-6.3 parts by weight; Preferably, the content of the vinyl acetate is 117-119 parts by weight, the content of the ethylene is 23-25 ​​parts by weight, and the content of the protective colloid is 5.8-6.1 parts by weight, which is equivalent to 100 parts by weight of water.

3. The composition according to claim 1 or 2, wherein, The polyvinyl alcohol includes partially hydrolyzed polyvinyl alcohol and completely hydrolyzed polyvinyl alcohol; Preferably, the weight ratio of the partially hydrolyzed polyvinyl alcohol to the completely hydrolyzed polyvinyl alcohol is 1:(0.2-0.5), more preferably 1:(0.3-0.4).

4. The composition according to any one of claims 1-3, wherein, The degree of polymerization of the polyvinyl alcohol is 500-1700, and the degree of alcoholysis is 88-99 mol%.

5. The composition according to any one of claims 1-4, wherein, The composition also includes a reducing agent, an oxidizing agent, and a pH adjuster; Preferably, the content of the reducing agent is 0.2-0.6 parts by weight, the content of the oxidizing agent is 0.3-0.7 parts by weight, and the content of the pH adjuster is 0.05-0.09 parts by weight, equivalent to 100 parts by weight of water. More preferably, the content of the reducing agent is 0.3-0.5 parts by weight, the content of the oxidizing agent is 0.4-0.6 parts by weight, and the content of the pH adjuster is 0.06-0.08 parts by weight, equivalent to 100 parts by weight of water.

6. The composition according to claim 5, wherein, The reducing agent is selected from one or more of ascorbic acid, isoascorbate, and tartrate; preferably, the reducing agent is selected from one or more of ascorbic acid, zinc isoascorbate, sodium isoascorbate, magnesium isoascorbate, zinc tartrate, sodium tartrate, and magnesium tartrate; more preferably, the reducing agent is selected from one or more of ascorbic acid, sodium isoascorbate, and potassium tartrate. And / or, the oxidant is an organic peroxide and / or an inorganic peroxide, preferably one or more of tert-butyl hydroperoxide, hydrogen peroxide, potassium persulfate and ammonium persulfate; And / or, the pH adjuster is selected from one or more of bicarbonate, acetate, phosphate and sodium hydroxide, preferably sodium hydroxide.

7. A method for preparing a vinyl acetate-ethylene copolymer emulsion for textiles using the composition according to any one of claims 1-6, characterized in that, The method includes: (1) Mix and stir a portion of vinyl acetate, ethylene, protective colloid and water; (2) Add the first part of oxidant and the first part of reducing agent to the product obtained in step (1) to carry out the first reaction; (3) Add another part of vinyl acetate, ethylene, a second part of oxidant, and a second part of reducing agent to the product obtained in step (2) to carry out a second reaction; (4) Add the remaining oxidant and the remaining reducing agent to the product obtained in step (3) for post-treatment, then add pH adjuster, discharge, and filter to obtain vinyl acetate-ethylene copolymer emulsion for textiles.

8. The method according to claim 7, wherein, The conditions for the first reaction include: a temperature of 50-54℃ and a pressure of 3.6-3.9 MPa; And / or, the conditions for the second reaction include: a temperature of 75-85°C and a pressure of 5.2-6 MPa; And / or, when the temperature is 75-85℃ and the ethylene pressure rises to 5.2-6MPa, another portion of vinyl acetate is added to carry out a second reaction; And / or, the post-processing conditions include: a temperature of 70-80°C and a pressure of 1.5-5.5 MPa; And / or, the weight ratio of the portion of vinyl acetate to the other portion of vinyl acetate is (0.7-2.3):1; And / or, the weight ratio of the first portion of oxidant to the second portion of oxidant and the remaining oxidant is 1:(0.9-1.2):(1.9-2.2); And / or, the weight ratio of the first portion of reducing agent to the second portion of reducing agent and the remaining reducing agent is 1:(0.9-1.2):(1.9-2.2).

9. A vinyl acetate-ethylene copolymer emulsion for textiles prepared by the method of claim 7 or 8.

10. The use of the vinyl acetate-ethylene copolymer emulsion of claim 9 in textiles as one or more of coatings, slurries and adhesives.

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