Copolymer emulsion composition for building, copolymer emulsion for building, and preparation method and application of copolymer emulsion

Abstract

The invention relates to the field of buildings, and discloses a copolymerized emulsion composition for buildings, a copolymerized emulsion for buildings and a preparation method and application of the copolymerized emulsion composition, the copolymerized emulsion composition for buildings comprises vinyl acetate, ethylene, an emulsifier, a protective colloid and water, the protective colloid is polyvinyl alcohol and is equivalent to 100 parts by weight of water, the content of the vinyl acetate is 111-117 parts by weight, and the content of the ethylene is 0.1-0.5 part by weight. The content of the ethylene is 23-28 parts by weight, the content of the emulsifier is 0.7-1.4 parts by weight, and the content of the protective colloid is 6-7 parts by weight. Through the specific protective colloid and the emulsifier, the elongation of the waterproof coating can be improved.

Description

Technical Field

[0001] This invention relates to the field of construction, specifically to a copolymer emulsion composition for construction, a copolymer emulsion for construction, 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 the construction industry in cement, concrete, interior and exterior wall coatings, building adhesives, roof and floor waterproofing, fireproof coatings, rust removal coatings, interface agents, joint caulking agents, and cement mortar modifiers.

[0004] Existing technologies have conducted extensive research on improving the elongation at break of cementitious building materials.

[0005] CN106243845B discloses a transparent, fast-setting, environmentally friendly building waterproof coating, characterized by comprising component A and component B. Component A is prepared from the following raw materials in parts by weight: 85-96 parts EVA emulsion, 12-18 parts transparent quartz glass powder, 0.24-0.6 parts dodecyl alcohol ester, 0.6-1.2 parts stabilizer, 0.24-0.36 parts dispersant, 0.24-0.36 parts defoamer, 0.18-0.3 parts bactericide, and 6-18 parts water. Component B is prepared from the following raw materials in parts by weight: 18-30 parts fast-setting agent, 3-9.6 parts accelerator, and 5-15 parts water. Component A uses transparent EVA emulsion as the main film-forming substance, and component B uses a liquid alkali-free fast-setting agent and a nano-film-forming accelerator as curing agents. After component A and component B come into contact and react, they rapidly solidify to form a transparent waterproof layer. The waterproof layer has high tensile strength and elongation, but specific test data is unavailable.

[0006] CN116179042B discloses a highly elastic, low-temperature resistant waterproof coating, its preparation method, and its application. This waterproof coating comprises a triblock or pentablock copolymer with A-block end groups formed from monomers A and B. According to the FOX equation, the glass transition temperature of the A-block is 10-40℃, and the glass transition temperature of the B-block is -70℃ to -40℃. Monomer A includes styrene and one or a combination of two of butyl acrylate and isooctyl acrylate, while B includes butyl acrylate and / or isooctyl acrylate. Through block structure design, using a hard-soft-hard-soft-hard pentablock structure, the elongation at break of the final polymer is improved (not less than 800%).

[0007] CN113248190A discloses an ultra-flexible nano-modified polymer cement-based waterproof coating and its preparation method. This nano-modified polymer cement-based waterproof coating comprises a liquid component and a cement-based powder component. By weight, the liquid component mainly comprises: 100 parts styrene-acrylic emulsion, 10-20 parts water, 0.025-0.1 parts nanoparticles, 0.25-1.0 parts alkaline agent, and 0.25-1.0 parts defoamer. The cement-based component comprises hydraulic cement and inactive fillers. The addition of hydrophilic nanoparticles and a silane coupling agent nano-modifies the emulsion, enhancing the elasticity of the waterproof coating.

[0008] CN117467085A discloses a vinyl acetate-ethylene copolymer emulsion for coatings and its preparation method. This method employs a two-step polymerization process to synthesize the vinyl acetate-ethylene copolymer emulsion. The key feature is that the ethylene pressure in the first polymerization step is ≤2.0 MPa, and the ethylene pressure in the second polymerization step is ≥4.0 MPa. The emulsion adopts a "hard core, soft shell" core-shell structure, and after drying and forming a film, it simultaneously possesses high tensile strength and high elongation at break (up to 110%).

[0009] However, the above methods, which aim to improve the elongation at break of waterproof coatings by adding film-forming aids, nano-modification, and block or core-shell structure design, have disadvantages such as high cost, complex process, and poor environmental performance.

[0010] Therefore, researching and developing a copolymer emulsion for construction is of great significance. Summary of the Invention

[0011] The purpose of this invention is to overcome the problem of high cost in the prior art, and to provide a copolymer emulsion composition for construction, a copolymer emulsion for construction, a preparation method thereof, and its application. This invention, through specific protective colloids and emulsifiers, can improve the elongation of waterproof coatings.

[0012] To achieve the above objectives, a first aspect of the present invention provides a copolymer emulsion composition for construction, wherein the composition comprises vinyl acetate, ethylene, an emulsifier, 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 111-117 parts by weight, the content of ethylene is 23-28 parts by weight, the content of the emulsifier is 0.7-1.4 parts by weight, and the content of the protective colloid is 6-7 parts by weight.

[0013] A second aspect of the present invention provides a method for preparing a copolymer emulsion for construction using the aforementioned copolymer emulsion composition for construction, wherein the method comprises:

[0014] (1) Mix a portion of vinyl acetate, emulsifier, protective colloid and water, and pressurize with ethylene;

[0015] (2) Add the first part of the oxidant and the first part of the reducing agent to the product obtained in step (1) and carry out the first reaction;

[0016] (3) The remaining vinyl acetate, ethylene, the second part of the oxidant, and the second part of the reducing agent are continuously added to the product obtained in step (2) to carry out the second reaction;

[0017] (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 a copolymer emulsion for construction.

[0018] A third aspect of the present invention provides a copolymer emulsion for construction prepared by the method described above.

[0019] The fourth aspect of the present invention provides an application of the aforementioned copolymer emulsion for construction as one or more of coatings, slurries, adhesives, interface agents and modifiers in the construction field.

[0020] Through the above technical solution, the present invention has the following beneficial effects:

[0021] (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.

[0022] (2) The protective colloid used in this invention is inexpensive, and the production cost of VAE products is low. Detailed Implementation

[0023] 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.

[0024] As previously stated, the first aspect of the present invention provides a copolymer emulsion composition for construction, wherein the composition comprises vinyl acetate, ethylene, an emulsifier, 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 111-117 parts by weight, the content of ethylene is 23-28 parts by weight, the content of the emulsifier is 0.7-1.4 parts by weight, and the content of the protective colloid is 6-7 parts by weight.

[0025] According to the present invention, preferably, the content of vinyl acetate is 112-116 parts by weight (equivalent to 100 parts by weight of water), the content of ethylene is 24-27 parts by weight, the content of emulsifier is 0.8-1.3 parts by weight, and the content of protective colloid is 6.2-6.8 parts by weight; more preferably, the content of vinyl acetate is 113-115 parts by weight (equivalent to 100 parts by weight of water), the content of ethylene is 25-26 parts by weight, the content of emulsifier is 1-1.1 parts by weight, and the content of protective colloid is 6.4-6.6 parts by weight. In the present invention, limiting the content of vinyl acetate, ethylene, emulsifier, protective colloid, and water within the aforementioned ranges can achieve a film that is both soft and strong; if the ethylene content is too high, the film will lack strength; if the ethylene content is too low, the film will lack softness.

[0026] The inventors of this invention discovered that ethylene, as a soft monomer, can lower the glass transition temperature of VAE (vapor-based adhesive) and improve the flexibility of the film. Regarding the strength of cement itself, the technical solution of this invention, using specific protective colloids and emulsifiers, can improve the elongation of the waterproof coating without reducing its tensile strength.

[0027] 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:(0.5-0.8), more preferably 1:(0.6-0.7). In the present invention, limiting the weight ratio of the partially hydrolyzed polyvinyl alcohol to the fully hydrolyzed polyvinyl alcohol within the aforementioned range results in improved elongation due to the absence of ester-active groups in fully hydrolyzed polyvinyl alcohol and fewer contact points with cement during VAE emulsion film formation. If the weight ratio of the partially hydrolyzed polyvinyl alcohol to the fully hydrolyzed polyvinyl alcohol is too high, the waterproof material will have low elongation; if the weight ratio is too low, the waterproof material will have low tensile strength.

[0028] 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 1799.

[0029] According to the present invention, the emulsifier is selected from one or more of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, preferably octylphenol polyoxyethylene ether.

[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 0.3-0.7 parts by weight, the content of the oxidizing agent is 0.3-0.6 parts by weight, and the content of the pH adjuster is 0.07-0.1 parts by weight, equivalent to 100 parts by weight of water; preferably, the content of the reducing agent is 0.4-0.6 parts by weight, the content of the oxidizing agent is 0.4-0.5 parts by weight, and the content of the pH adjuster is 0.08-0.09 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 copolymer emulsion for construction using the aforementioned composition, wherein the method comprises:

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

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

[0042] (3) The remaining vinyl acetate, ethylene, the second part of the oxidant, and the second part of the reducing agent are continuously added to the product obtained in step (2) to carry out the 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 a copolymer emulsion for construction.

[0044] According to the present invention, the conditions for the first reaction include: a temperature of 52-55°C and a pressure of 3.5-3.8 MPa; preferably, a temperature of 53-54°C and a pressure of 3.6-3.7 MPa.

[0045] According to the present invention, the conditions for the second reaction include: a temperature of 75-85°C and a pressure of 5.5-6.0 MPa; preferably, a temperature of 79-83°C and a pressure of 5.7-5.8 MPa.

[0046] According to the present invention, when the temperature is 75-85°C and the ethylene pressure rises to 5.5-6.0 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 73-77°C and a pressure of 2.5-4.0 MPa.

[0048] According to the present invention, the weight ratio of the portion of vinyl acetate to the other portion of vinyl acetate is (0.7-1.5):1, preferably (1.0-1.2):1.

[0049] According to the present invention, the weight ratio of the first oxidant, the second oxidant and the remaining oxidant is 1:(0.8-1.1):(1.8-2.1), preferably 1:(0.9-1.0):(1.9-2.0).

[0050] According to the present invention, the weight ratio of the first reducing agent, the second reducing agent and the remaining reducing agent is 1:(0.8-1.1):(1.8-2.1), preferably 1:(0.9-1.0):(1.9-2.0).

[0051] A third aspect of the present invention provides a copolymer emulsion for construction prepared by the method described above.

[0052] The fourth aspect of the present invention provides an application of the aforementioned copolymer emulsion for construction as one or more of coatings, slurries, adhesives, interface agents and modifiers in the construction field.

[0053] According to the present invention, the copolymer emulsion for building applications can be used in one or more of cement, concrete, interior and exterior wall coatings, building adhesives, roof and floor waterproofing, fireproof coatings, rust removal coatings, interface agents, joint caulking interface agents and cement mortar modifiers.

[0054] According to a particularly preferred embodiment of the present invention, a method for preparing a copolymer emulsion for construction 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, protective colloid, and emulsifier. After stirring evenly, add 45-70 parts of vinyl acetate monomer, and raise the temperature and pressure. When the temperature reaches 52-55℃ and the pressure reaches 3.5-3.8MPa, simultaneously add 0.1-0.2 parts of oxidant and 0.1-0.23 parts of reducing agent. When the temperature reaches 75-85℃ and the ethylene pressure rises to 5.5-6.0MPa, add 41-72 parts of vinyl acetate monomer over 60-150 minutes, continuously adding 0.12-0.24 parts of oxidant and 0.11-0.25 parts of reducing agent. After the monomer addition is complete, enter the finishing stage. After degassing, continuously add 0.08-0.16 parts of oxidant and 0.09-0.22 parts of reducing agent over 60 minutes. Then cool down, add pH adjuster and bactericide, and discharge, filter, and package.

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

[0063] Vinyl acetate: 111-117 parts;

[0064] Ethylene: 23-28 parts;

[0065] Protective colloid: 6-7 parts;

[0066] Emulsifier: 0.7-1.4 parts;

[0067] Reducing agent: 0.3-0.7 parts;

[0068] Oxidizing agent: 0.3-0.6 parts;

[0069] pH adjuster: 0.07-0.10 parts;

[0070] Water: 100 portions.

[0071] The present invention will be described in detail below through embodiments.

[0072] In the following examples and comparative examples:

[0073] Samples were prepared and untreated tensile properties were tested according to GB / T 23445-2009 standard for polymer cement waterproof coatings.

[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 preparation of a copolymer emulsion for construction using the method of the present invention.

[0077] (1) While stirring, add 100 parts of deionized water, 2.3 parts of PVA1788, 1.7 parts of PVA0588, 2.4 parts of PVA1799, and 1.0 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 57 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0078] (2) When the temperature rises to 53℃ and the pressure reaches 3.7MPa, add 0.1 parts of tert-butyl hydrogen peroxide and 0.1 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 79℃ and the ethylene pressure rises to 5.8MPa, add the remaining 56 parts of vinyl acetate monomer, 0.09 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 73℃ and the pressure reaches 3.0MPa, and the finishing period begins.

[0079] (3) After degassing to the degassing tank, add 0.21 parts of tert-butyl hydrogen peroxide and 0.21 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 a copolymer emulsion for building.

[0080] Example 2

[0081] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0082] (1) While stirring, add 100 parts of deionized water, 2.1 parts of PVA1788, 1.8 parts of PVA0588, 2.6 parts of PVA1799, and 1.1 parts of emulsifier nonylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 52 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0083] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.11 parts of tert-butyl hydrogen peroxide and 0.13 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 81℃ and the ethylene pressure rises to 5.7MPa, add the remaining 62 parts of vinyl acetate monomer, 0.10 parts of continuous tert-butyl hydrogen peroxide, and 0.12 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 75℃ and the pressure reaches 4.0MPa, and the finishing period begins.

[0084] (3) After degassing to the degassing tank, add 0.29 parts of tert-butyl hydrogen peroxide and 0.25 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 a copolymer emulsion for building.

[0085] Example 3

[0086] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0087] (1) While stirring, add 100 parts of deionized water, 2.0 parts of PVA1788, 1.9 parts of PVA0588, 2.7 parts of PVA1799, and 1.0 parts of emulsifier fatty alcohol polyoxyethylene ether to the reactor. After stirring evenly, add 62 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0088] (2) When the temperature rises to 53℃ and the pressure reaches 3.6MPa, add 0.13 parts of tert-butyl hydrogen peroxide and 0.15 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 83℃ and the ethylene pressure rises to 5.7MPa, add the remaining 53 parts of vinyl acetate monomer, 0.13 parts of continuous tert-butyl hydrogen peroxide, and 0.15 parts of continuous ascorbic acid within 90 minutes. After the continuous addition of vinyl acetate monomer is completed, the temperature reaches 77℃ and the pressure reaches 2.5MPa, and the finishing period begins.

[0089] (3) After degassing to the degassing tank, add 0.24 parts of tert-butyl hydrogen peroxide and 0.3 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 a copolymer emulsion for building.

[0090] Example 4

[0091] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0092] (1) While stirring, add 100 parts of deionized water, 2.1 parts of PVA1788, 1.7 parts of PVA0588, 2.4 parts of PVA1799, and 1.3 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 53 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0093] (2) When the temperature rises to 53℃ and the pressure reaches 3.7MPa, add 0.10 parts of tert-butyl hydrogen peroxide and 0.10 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 77℃ and the ethylene pressure rises to 5.9MPa, add the remaining 59 parts of vinyl acetate monomer, 0.09 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 4.5MPa, and the finishing period begins.

[0094] (3) After degassing to the degassing tank, add 0.11 parts of tert-butyl hydrogen peroxide and 0.11 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 a copolymer emulsion for building.

[0095] Example 5

[0096] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0097] (1) While stirring, add 100 parts of deionized water, 2.2 parts of PVA1788, 1.8 parts of PVA0588, 2.8 parts of PVA1399 and 0.8 parts of emulsifier octylphenol polyoxyethylene ether to the reactor, stir evenly, add 65 parts of vinyl acetate monomer, and then heat and pressurize.

[0098] (2) When the temperature rises to 54℃ and the pressure reaches 3.6MPa, add 0.12 parts of tert-butyl hydrogen peroxide and 0.15 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 84℃ and the ethylene pressure rises to 5.6MPa, add the remaining 51 parts of vinyl acetate monomer, 0.11 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 78℃ and the pressure reaches 2.0MPa, and the finishing period begins.

[0099] (3) After degassing to the degassing tank, add 0.27 parts of tert-butyl hydrogen peroxide and 0.32 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 a copolymer emulsion for building.

[0100] Example 6

[0101] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0102] (1) While stirring, add 100 parts of deionized water, 2.3 parts of PVA1788, 1.7 parts of PVA0588, 2.0 parts of PVA1799, and 1.4 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 46 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0103] (2) When the temperature rises to 52℃ and the pressure reaches 3.8MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.11 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 65 parts of vinyl acetate monomer, 0.07 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 70℃ and the pressure reaches 5.5MPa, and the finishing period begins.

[0104] (3) After degassing to the degassing tank, add 0.15 parts of tert-butyl hydrogen peroxide and 0.20 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 a copolymer emulsion for building.

[0105] Example 7

[0106] This embodiment illustrates the preparation of a copolymer emulsion for construction using the method of the present invention.

[0107] (1) While stirring, add 100 parts of deionized water, 2.3 parts of PVA1788, 1.6 parts of PVA0588, 3.1 parts of PVA1799 and 0.7 parts of emulsifier octylphenol polyoxyethylene ether to the reactor, stir evenly, add 70 parts of vinyl acetate monomer, and then heat and pressurize.

[0108] (2) When the temperature rises to 55℃ and the pressure reaches 3.5MPa, add 0.14 parts of tert-butyl hydrogen peroxide and 0.11 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 5.5MPa, add the remaining 47 parts of vinyl acetate monomer, 0.16 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 80℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0109] (3) After degassing to the degassing tank, add 0.30 parts of tert-butyl hydrogen peroxide and 0.36 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.10 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare a copolymer emulsion for building.

[0110] Comparative Example 1

[0111] (1) While stirring, add 100 parts of deionized water, 3.3 parts of PVA1788, 2.6 parts of PVA0588, 3.1 parts of PVA1799, and 0.5 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 70 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0112] (2) When the temperature rises to 55℃ and the pressure reaches 3.5MPa, add 0.14 parts of tert-butyl hydrogen peroxide and 0.11 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 85℃ and the ethylene pressure rises to 5.5MPa, add the remaining 47 parts of vinyl acetate monomer, 0.16 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 80℃ and the pressure reaches 1.5MPa, and the finishing period begins.

[0113] (3) After degassing to the degassing tank, add 0.30 parts of tert-butyl hydrogen peroxide and 0.36 parts of ascorbic acid for post-treatment; after cooling after post-treatment, add 0.10 parts of pH adjuster, bactericide, etc., discharge, filter, and package; prepare copolymer emulsion.

[0114] Comparative Example 2

[0115] (1) While stirring, add 100 parts of deionized water, 1.9 parts of PVA1788, 1.7 parts of PVA0588, 1.8 parts of PVA1799, and 0.3 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 56 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0116] (2) When the temperature rises to 52℃ and the pressure reaches 3.8MPa, add 0.08 parts of tert-butyl hydrogen peroxide and 0.11 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 65 parts of vinyl acetate monomer, 0.07 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 70℃ and the pressure reaches 5.5MPa, and the finishing period begins.

[0117] (3) After degassing to the degassing tank, add 0.15 parts of tert-butyl hydrogen peroxide and 0.20 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 copolymer emulsion.

[0118] Comparative Example 3

[0119] (1) While stirring, add 100 parts of deionized water, 2.2 parts of PVA1788, 1.8 parts of PVA0588, 2.8 parts of PVA1799, and 1.7 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 75 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 0.12 parts of tert-butyl hydrogen peroxide and 0.15 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 84℃ and the ethylene pressure rises to 5.6MPa, add the remaining 58 parts of vinyl acetate monomer, 0.11 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 78℃ and the pressure reaches 2.0MPa, and the finishing period begins.

[0121] (3) After degassing to the degassing tank, add 0.27 parts of tert-butyl hydrogen peroxide and 0.32 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 copolymer emulsion.

[0122] Comparative Example 4

[0123] (1) While stirring, add 100 parts of deionized water, 2.6 parts of PVA1788, 2.2 parts of PVA0588, 1.4 parts of PVA1799, and 1.3 parts of emulsifier octylphenol polyoxyethylene ether to the reactor. After stirring evenly, add 53 parts of vinyl acetate monomer, and then raise the temperature and pressure.

[0124] (2) When the temperature rises to 53℃ and the pressure reaches 3.7MPa, add 0.10 parts of tert-butyl hydrogen peroxide and 0.10 parts of ascorbic acid to the reactor. When the temperature inside the reactor reaches 77℃ and the ethylene pressure rises to 5.9MPa, add the remaining 59 parts of vinyl acetate monomer, 0.09 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 4.5MPa, and the finishing period begins.

[0125] (3) After degassing to the degassing tank, add 0.11 parts of tert-butyl hydrogen peroxide and 0.11 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 copolymer emulsion.

[0126] Test case

[0127] VAE emulsions were prepared using the methods of Examples 1-7 and Comparative Examples 1-4, and the elongation at break was tested, as shown in Table 1.

[0128] Table 1

[0129] Serial Number Elongation at break % Example 1 258 Example 2 237 Example 3 242 Example 4 210 Example 5 206 Example 6 199 Example 7 194 Comparative Example 1 149 Comparative Example 2 160 Comparative Example 3 155 Comparative Example 4 120

[0130] As shown in Table 1, the emulsion prepared according to the present invention was tested for elongation at break of the waterproof coating using the national standard method. The elongation at break of Examples 1-7 of the present invention was improved compared with that of Comparative Examples 1-4; this proves that the method used in the present invention can improve the elongation at break of VAE waterproof coatings with low production cost and simple method.

[0131] 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 copolymer emulsion composition for construction, characterized in that, The composition comprises vinyl acetate, ethylene, emulsifier, 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 111-117 parts by weight, the content of ethylene is 23-28 parts by weight, the content of emulsifier is 0.7-1.4 parts by weight, and the content of protective colloid is 6-7 parts by weight.

2. The composition according to claim 1, comprising 100 parts by weight of water, wherein the content of vinyl acetate is 112-116 parts by weight, the content of ethylene is 24-27 parts by weight, the content of emulsifier is 0.8-1.3 parts by weight, and the content of protective colloid is 6.2-6.8 parts by weight; Preferably, the content of the vinyl acetate is 113-115 parts by weight, the content of the ethylene is 25-26 parts by weight, the content of the emulsifier is 1-1.1 parts by weight, and the content of the protective colloid is 6.4-6.6 parts by weight, 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:(0.5-0.8), more preferably 1:(0.6-0.7); Preferably, the degree of polymerization of the polyvinyl alcohol is 500-1700, and the degree of alcoholysis is 88-99 mol%.

4. The composition according to any one of claims 1-3, wherein, The emulsifier is selected from one or more of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

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 0.3-0.7 parts by weight, the content of the oxidizing agent is 0.3-0.6 parts by weight, and the content of the pH adjuster is 0.07-0.1 parts by weight, equivalent to 100 parts by weight of water. More preferably, the content of the reducing agent is 0.4-0.6 parts by weight, the content of the oxidizing agent is 0.4-0.5 parts by weight, and the content of the pH adjuster is 0.08-0.09 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 copolymer emulsion for construction using the copolymer emulsion composition for construction according to any one of claims 1-6, characterized in that, The method includes: (1) Mix a portion of vinyl acetate, emulsifier, protective colloid and water, and pressurize with ethylene; (2) Add the first part of the oxidant and the first part of the reducing agent to the product obtained in step (1) and carry out the first reaction; (3) The remaining vinyl acetate, ethylene, the second part of the oxidant, and the second part of the reducing agent are continuously added to the product obtained in step (2) to carry out the 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 a copolymer emulsion for construction.

8. The method according to claim 7, wherein, The conditions for the first reaction include: a temperature of 52-55℃ and a pressure of 3.5-3.8 MPa; And / or, the conditions for the second reaction include: a temperature of 75-85°C and a pressure of 5.5-6 MPa; And / or, when the temperature is 75-85℃ and the ethylene pressure rises to 5.5-6MPa, 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 (0.7-1.5):1; And / or, the weight ratio of the first portion of oxidant, the second portion of oxidant, and the remaining oxidant is 1:(0.8-1.1):(1.8-2.1); And / or, the weight ratio of the first reducing agent, the second reducing agent and the remaining reducing agent is 1:(0.8-1.1):(1.8-2.1).

9. A copolymer emulsion for construction prepared by the method of claim 7 or 8.

10. The application of the copolymer emulsion for construction as claimed in claim 9 in the construction field as one or more of coatings, slurries, adhesives, interface agents and modifiers.