Basefilm emulsion with formaldehyde removal function and preparation method thereof

Abstract

The invention relates to the technical field of basement membrane emulsions, in particular to a basement membrane emulsion with an aldehyde removal function and a preparation method thereof.According to the basement membrane emulsion with the aldehyde removal function, an anionic emulsifier and a nonionic emulsifier are used in cooperation, the stability of emulsion particles can be improved, the used emulsifier can form a thick hydration layer, and the stability of the emulsion particles is improved; a good effect is achieved on the stability of latex particles; secondly, monomers, namely self-made adipic dihydrazide and self-made 3-hydroxybutenoic acid-2-ethylene methacrylate, capable of removing formaldehyde are compounded and then grafted to an acrylate polymer chain, so that the basic performance of the original emulsion is not influenced while functional groups for absorbing formaldehyde are retained; on the basis of improving the formaldehyde removal capability of the base film emulsion, the stability and durability of the self-made adipic dihydrazide and the self-made 3-hydroxybutenoic acid-2-ethylene methacrylate monomer can be improved, so that the base film emulsion can continuously play a role in removing formaldehyde in practical application.

Description

Technical Field

[0001] The invention relates to the technical field of base film emulsions, and in particular to a base film emulsion with formaldehyde removal function and a preparation method thereof. Background Art

[0002] Wallpaper base film is a special alkali-resistant, moisture-proof and mildew-proof wall treatment material, which can effectively prevent moisture and alkaline substances from seeping out of the construction wall, and prevent wall decoration materials such as wallpaper and decorative panels from getting damp, getting moldy and turning black and discolored. The wallpaper base film on the market has a single function, cannot inhibit the mildew of wallpaper glue, and has no lasting antibacterial effect. Ordinary wallpaper base film used on powdered walls will cause large-scale wallpaper shedding, and will release some harmful organic gases, polluting the environment and causing harm to human health.

[0003] After a new house is renovated, a large amount of formaldehyde is contained in the room, which can cause damage to human health. This has aroused people's concern about the safety performance of decorative materials including coatings. Therefore, how to provide a wallpaper base film emulsion that can prevent mildew and moisture, solidify the wall and has the function of removing formaldehyde has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0004] Technical issues solved In view of the above-mentioned shortcomings of the prior art, the present invention provides a base film emulsion with formaldehyde removal function and a preparation method thereof, which can effectively solve the problem that the wallpaper base film in the prior art does not have the function of removing formaldehyde.

[0005] Technical Solution To achieve the above objectives, the present invention is implemented through the following technical solutions: A base film emulsion with formaldehyde removal function, the base film emulsion with formaldehyde removal function is composed of the following components: distilled water, an alkyl acrylate component, an acrylic acid hydrophilic monomer component, a formaldehyde removal monomer component, a cross-linking monomer component, an emulsifier component, an initiator component, an oxidant component, a reducing agent component, a pH regulator component and an antifreeze component; The formaldehyde-removing functional monomer component is prepared by mixing self-made adipic acid dihydrazide and self-made 3-hydroxybutenoic acid-2-methylacrylate in an equal weight ratio.

[0006] Furthermore, the alkyl acrylate component is at least one of methyl methacrylate, isooctyl acrylate, ethyl acrylate, butyl acrylate, styrene and acrylonitrile.

[0007] Furthermore, the acrylic hydrophilic monomer component is at least one of acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl acrylate and hydroxyethyl methacrylate.

[0008] Furthermore, the preparation steps of the homemade adipic acid dihydrazide are: Step 1, weighing a calculated amount of adipic acid and anhydrous methanol in a molar ratio of 1:4 and adding them into a flask, then adding a catalyst of potassium hydrogen sulfate with a weight of 6% of adipic acid and heating to reflux, reflux reaction for 1 hour, and then placing it at 68°C for 2 hours, and then collecting the fraction at 110°C / 1.87kPa, and the obtained fraction is recorded as dimethyl adipate; Step 2, weigh the calculated amount of dimethyl adipate, hydrazine hydrate and anhydrous methanol in a molar ratio of 1:4:4 and pour them into a flask, react at room temperature for 2 hours, cool and crystallize in an ice water bath, filter and wash with deionized water for 3 times, and dry at 42°C for 3 hours to obtain the self-made adipic acid dihydrazide.

[0009] Furthermore, the preparation steps of the homemade 3-hydroxybutenoic acid-2-methylacrylate are as follows: Step 1, weigh 0.5g of hydroquinone and pour it into a flask, stir and heat it to 90°C at a stirring speed of 300r / min, then introduce ethylene oxide gas under nitrogen protection to react for 2h, cool to 60°C after the reaction, and obtain hydroxyethyl methacrylate after reduced pressure distillation; Step 2: Weigh 39 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone into a flask, stir and react under nitrogen protection at a temperature of 5°C, add 25 g of diethylene ketone at a dropping rate of 1 drop / s under stirring conditions of a stirring speed of 300 r / min, then react at a water bath temperature of 50°C for 5 hours, and obtain homemade 3-hydroxybutenoic acid-2-methylacrylate after reduced pressure distillation.

[0010] Furthermore, the crosslinking monomer component is at least one of vinyl trimethoxysilane, vinyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, trimethylolpropane trimethacrylate, allyl methacrylate and divinylbenzene.

[0011] Furthermore, the emulsifier component is prepared by mixing an anionic emulsifier and a nonionic emulsifier in a weight ratio of 1-5:1-5, the anionic emulsifier is at least one of isomeric tridecyl alcohol sulfate sodium salt, sodium succinic acid sulfonate, 2-acrylamido-2-methylpropane sulfonate, 3-allyloxy-1-hydroxy-propane phosphate, sodium vinyl sulfonate and fatty alcohol ether vinyl sulfonic acid sodium salt, and the nonionic emulsifier is at least one of polyoxyethylene sorbitan monooleate, fatty alcohol ethoxylate and alkyl ethoxylate.

[0012] Furthermore, the initiator component is at least one of potassium persulfate, ammonium persulfate and sodium persulfate; the oxidant component is at least one of tert-butyl hydroperoxide and hydrogen peroxide; and the reductant component is at least one of sodium bisulfite and vitamin C.

[0013] Furthermore, the pH regulator component is a sodium hydroxide solution with a mass fraction of 10%; the antifreeze component is at least one of calcium chloride, methanol, ethanol, ethylene glycol, propylene glycol, glycerol and polyethylene glycol.

[0014] A method for preparing a base film emulsion with formaldehyde removal function, the preparation method comprising: S1, weigh 0.5-4 parts by weight of emulsifier component and 20-80 parts by weight of distilled water and add them into an emulsifying tank, stir at a stirring speed of 300r / min for 10min, then add 30-80 parts by weight of alkyl acrylate component, 0.5-3 parts by weight of acrylic acid hydrophilic monomer component, 3-20 parts by weight of aldehyde-removing functional monomer component, 0.05-0.2 parts by weight of cross-linking monomer component and 0.1-0.5 parts by weight of initiator component, then stir at the original stirring speed for 15-30min, the result is recorded as pre-emulsion; S2, weighing 0.5-1 parts by weight of emulsifier component and 60-120 parts by weight of distilled water into a reactor, stirring at a stirring speed of 500r / min for 10min, heating to 70-90°C and adding 0.1-0.5 parts by weight of initiator component, stirring at the original stirring speed for 10min, adding 0.05-15% of the total amount of pre-emulsion, continuing to stir at the original stirring speed for 10-30min, the result is recorded as seed emulsion; S3, raising the temperature of the seed emulsion to 80-90°C and then dropping the remaining pre-emulsion, keeping the temperature at the original temperature for 30-60min after the addition is completed, then cooling to 70-80°C and dropping 0.1-0.3 parts by weight of the oxidant component and 0.1-0.3 parts by weight of the reductant component, the result is recorded as the reaction component; S4. Cool the reaction components to 50-70°C and add 0.1-0.3 parts by weight of an oxidant component and 0.1-0.3 parts by weight of a reductant component, cool the reaction components to 48°C again and add a pH adjuster component to adjust the pH value to 7-9, then add 1-10 parts by weight of an antifreeze component, stir at a stirring speed of 200 r / min for 5 minutes and filter. The result is a base film emulsion with formaldehyde removal function, the solid content of the base film emulsion with formaldehyde removal function is 20-40%, and the particle size is 0.1-0.4um.

[0015] Beneficial Effects The present invention provides a base film emulsion with formaldehyde removal function and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses anionic emulsifiers and nonionic emulsifiers in combination to increase the stability of latex particles. The emulsifiers used can form a thicker hydration layer, which has a good effect on the stability of latex particles. Secondly, the present invention compounded the self-made adipic acid dihydrazide and self-made 3-hydroxybutenoic acid-2-methylacrylate monomers with formaldehyde removal and grafted them onto the acrylic ester polymer chain, while retaining the functional groups that absorb formaldehyde, without affecting the basic properties of the original emulsion. The self-made adipic acid dihydrazide and the self-made 3-hydroxybutenoic acid-2-methylacrylate have good formaldehyde removal effects respectively, and the two can produce a synergistic effect after compounding. On the basis of improving the formaldehyde removal ability of the base film emulsion, the stability and durability of the self-made adipic acid dihydrazide and the self-made 3-hydroxybutenoic acid-2-methylacrylate monomers can also be improved, so that they can continue to play the role of removing formaldehyde in practical applications.

[0016] 2. The present invention adds an acrylic acid hydrophilic monomer. After being grafted onto the polymer, the hydrophilic end of the hydrophilic monomer will always remain on the surface of the latex particles, which can better protect the latex particles during the freeze-thaw process, thereby better protecting the emulsion; secondly, the present invention adds an antifreeze agent. Since the thickness of the base film emulsion applied to the wall is very thin, it is easy to penetrate into the wall, so that the wall surface cannot be solidified and the sealing effect cannot be achieved. After adding the antifreeze agent, the latex film can be effectively ensured to solidify on the wall surface, thereby achieving the effect of sealing the wall surface; therefore, the base film emulsion with formaldehyde removal function prepared by the present invention has a simple synthesis process, is easy to operate, has a low cost, is highly safe, and has an excellent market application prospect. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The present invention will be further described below in conjunction with the embodiments.

[0019] Example 1 The base film emulsion with formaldehyde removal function of the present embodiment is composed of the following components: distilled water, an alkyl acrylate component, an acrylic acid hydrophilic monomer component, a formaldehyde removal monomer component, a cross-linking monomer component, an emulsifier component, an initiator component, an oxidant component, a reducing agent component, a pH regulator component and an antifreeze component; The aldehyde-removing functional monomer component is prepared by mixing homemade adipic acid dihydrazide and homemade 3-hydroxybutenoic acid-2-methylacrylate ethylene glycol in equal weight ratios; Wherein, the preparation steps of homemade adipic acid dihydrazide are: Step 1, weighing a calculated amount of adipic acid and anhydrous methanol in a molar ratio of 1:4 and adding them into a flask, then adding a catalyst of potassium hydrogen sulfate with a weight of 6% of adipic acid and heating to reflux, reflux reaction for 1 hour, and then placing it at 68°C for 2 hours, and then collecting the fraction at 110°C / 1.87kPa, and the obtained fraction is recorded as dimethyl adipate; Step 2, weigh the calculated amount of dimethyl adipate, hydrazine hydrate and anhydrous methanol in a molar ratio of 1:4:4 and pour them into a flask, react at room temperature for 2 hours, cool and crystallize in an ice water bath, filter and wash with deionized water for 3 times, and dry at 42°C for 3 hours to obtain the self-made adipic acid dihydrazide.

[0020] The preparation steps of homemade 3-hydroxybutenoic acid-2-methylacrylate are as follows: Step 1, weigh 0.5g of hydroquinone and pour it into a flask, stir and heat it to 90°C at a stirring speed of 300r / min, then introduce ethylene oxide gas under nitrogen protection to react for 2h, cool to 60°C after the reaction, and obtain hydroxyethyl methacrylate after reduced pressure distillation; Step 2: Weigh 39 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone into a flask, stir and react under nitrogen protection at a temperature of 5°C, add 25 g of diethylene ketone at a dropping rate of 1 drop / s under stirring conditions of a stirring speed of 300 r / min, then react at a water bath temperature of 50°C for 5 hours, and obtain homemade 3-hydroxybutenoic acid-2-methylacrylate after reduced pressure distillation.

[0021] The alkyl acrylate component is prepared by mixing butyl acrylate and styrene in an equal weight ratio.

[0022] The acrylic hydrophilic monomer component is prepared by mixing acrylic acid and hydroxyethyl acrylate in an equal weight ratio.

[0023] The crosslinking monomer component is vinyltrimethoxysilane.

[0024] The emulsifier component is prepared by mixing an anionic emulsifier and a nonionic emulsifier in a weight ratio of 1:1. The anionic emulsifier is sodium salt of fatty alcohol ether vinyl sulfonate, and the nonionic emulsifier is fatty alcohol ethoxylate.

[0025] The initiator component is potassium persulfate; the oxidant component is tert-butyl hydroperoxide; and the reducing agent component is sodium bisulfite.

[0026] The pH regulator component is a sodium hydroxide solution with a mass fraction of 10%; the antifreeze component is ethylene glycol.

[0027] A method for preparing a base film emulsion with formaldehyde removal function, the preparation method comprising: S1, weigh 3 parts by weight of emulsifier component and 50 parts by weight of distilled water and add them into an emulsifying tank, stir at a stirring speed of 300r / min for 10min, then add 60 parts by weight of alkyl acrylate component, 2 parts by weight of acrylic acid hydrophilic monomer component, 12 parts by weight of aldehyde-removing functional monomer component, 0.1 parts by weight of cross-linking monomer component and 0.3 parts by weight of initiator component in sequence, then stir at the original stirring speed for 22min, the result is recorded as pre-emulsion; S2, weighing 0.8 parts by weight of emulsifier component and 90 parts by weight of distilled water into a reactor, stirring at a stirring speed of 500 r / min for 10 min, heating to 80°C and adding 0.3 parts by weight of initiator component, stirring at the original stirring speed for 10 min, adding 8% of the total amount of pre-emulsion, continuing to stir at the original stirring speed for 20 min, and the obtained solution is recorded as seed emulsion; S3, raising the temperature of the seed emulsion to 85°C and then dropping the remaining pre-emulsion, keeping the temperature at the original temperature for 45 minutes after the addition is completed, then cooling to 75°C and dropping 0.2 parts by weight of the oxidant component and 0.2 parts by weight of the reductant component, the result is recorded as the reaction component; S4. Cool the reaction components to 60°C and drop 0.2 parts by weight of the oxidant component and 0.2 parts by weight of the reductant component, cool again to 48°C and drop the pH adjuster component to adjust the pH value to 8, then add 5 parts by weight of the antifreeze component, stir at a stirring speed of 200 r / min for 5 minutes and filter, and the result is a base film emulsion with formaldehyde removal function.

[0028] Example 2 The base film emulsion with formaldehyde removal function of the present embodiment is composed of the following components: distilled water, an alkyl acrylate component, an acrylic acid hydrophilic monomer component, a formaldehyde removal monomer component, a cross-linking monomer component, an emulsifier component, an initiator component, an oxidant component, a reducing agent component, a pH regulator component and an antifreeze component; The aldehyde-removing functional monomer component is prepared by mixing homemade adipic acid dihydrazide and homemade 3-hydroxybutenoic acid-2-methylacrylate ethylene glycol in equal weight ratios; Wherein, the preparation steps of homemade adipic acid dihydrazide are: Step 1, weighing a calculated amount of adipic acid and anhydrous methanol in a molar ratio of 1:4 and adding them into a flask, then adding a catalyst of potassium hydrogen sulfate with a weight of 6% of adipic acid and heating to reflux, reflux reaction for 1 hour, and then placing it at 68°C for 2 hours, and then collecting the fraction at 110°C / 1.87kPa, and the obtained fraction is recorded as dimethyl adipate; Step 2, weigh the calculated amount of dimethyl adipate, hydrazine hydrate and anhydrous methanol in a molar ratio of 1:4:4 and pour them into a flask, react at room temperature for 2 hours, cool and crystallize in an ice water bath, filter and wash with deionized water for 3 times, and dry at 42°C for 3 hours to obtain the self-made adipic acid dihydrazide.

[0029] The preparation steps of homemade 3-hydroxybutenoic acid-2-methylacrylate are as follows: Step 1, weigh 0.5g of hydroquinone and pour it into a flask, stir and heat it to 90°C at a stirring speed of 300r / min, then introduce ethylene oxide gas under nitrogen protection to react for 2h, cool to 60°C after the reaction, and obtain hydroxyethyl methacrylate after reduced pressure distillation; Step 2: Weigh 39 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone into a flask, stir and react under nitrogen protection at a temperature of 5°C, add 25 g of diethylene ketone at a dropping rate of 1 drop / s under stirring conditions of a stirring speed of 300 r / min, then react at a water bath temperature of 50°C for 5 hours, and obtain homemade 3-hydroxybutenoic acid-2-methylacrylate after reduced pressure distillation.

[0030] The alkyl acrylate component is prepared by mixing methyl methacrylate and butyl acrylate in an equal weight ratio.

[0031] The acrylic hydrophilic monomer component is prepared by mixing acrylic acid and hydroxyethyl acrylate in an equal weight ratio.

[0032] The crosslinking monomer component is vinyltrimethoxysilane.

[0033] The emulsifier component is prepared by mixing an anionic emulsifier and a nonionic emulsifier in a weight ratio of 5:1. The anionic emulsifier is sodium salt of fatty alcohol ether vinyl sulfonate, and the nonionic emulsifier is fatty alcohol ethoxylate.

[0034] The initiator component is potassium persulfate; the oxidant component is tert-butyl hydroperoxide; and the reducing agent component is vitamin C.

[0035] The pH regulator component is a sodium hydroxide solution with a mass fraction of 10%; the antifreeze component is propylene glycol.

[0036] A method for preparing a base film emulsion with formaldehyde removal function, the preparation method comprising: S1, weigh 0.5 parts by weight of emulsifier component and 20 parts by weight of distilled water and add them into an emulsifying tank, stir at a stirring speed of 300r / min for 10min, then add 30 parts by weight of alkyl acrylate component, 0.5 parts by weight of acrylic acid hydrophilic monomer component, 3 parts by weight of aldehyde-removing functional monomer component, 0.05 parts by weight of cross-linking monomer component and 0.1 parts by weight of initiator component in sequence, then stir at the original stirring speed for 15min, the result is recorded as pre-emulsion; S2, weighing 1 part by weight of the emulsifier component and 120 parts by weight of distilled water into a reactor, stirring at a stirring speed of 500 r / min for 10 min, heating to 90°C and adding 0.5 parts by weight of the initiator component, stirring at the original stirring speed for 10 min, adding 15% of the total amount of the pre-emulsion, continuing to stir at the original stirring speed for 30 min, and the result is recorded as the seed emulsion; S3, raising the temperature of the seed emulsion to 80°C and then dropping the remaining pre-emulsion, keeping the temperature at the original temperature for 30 minutes after the addition is completed, then cooling to 70°C and dropping 0.1 parts by weight of the oxidant component and 0.1 parts by weight of the reductant component, the result is recorded as the reaction component; S4. Cool the reaction components to 50°C and drop 0.1 parts by weight of the oxidant component and 0.1 parts by weight of the reductant component, cool again to 48°C and drop the pH adjuster component to adjust the pH value to 7, then add 1 part by weight of the antifreeze component, stir at a stirring speed of 200 r / min for 5 minutes and filter, and the result is a base film emulsion with formaldehyde removal function.

[0037] Example 3 The base film emulsion with formaldehyde removal function of the present embodiment is composed of the following components: distilled water, an alkyl acrylate component, an acrylic acid hydrophilic monomer component, a formaldehyde removal monomer component, a cross-linking monomer component, an emulsifier component, an initiator component, an oxidant component, a reducing agent component, a pH regulator component and an antifreeze component; The aldehyde-removing functional monomer component is prepared by mixing homemade adipic acid dihydrazide and homemade 3-hydroxybutenoic acid-2-methylacrylate ethylene glycol in equal weight ratios; Wherein, the preparation steps of homemade adipic acid dihydrazide are: Step 1, weighing a calculated amount of adipic acid and anhydrous methanol in a molar ratio of 1:4 and adding them into a flask, then adding a catalyst of potassium hydrogen sulfate with a weight of 6% of adipic acid and heating to reflux, reflux reaction for 1 hour, and then placing it at 68°C for 2 hours, and then collecting the fraction at 110°C / 1.87kPa, and the obtained fraction is recorded as dimethyl adipate; Step 2, weigh the calculated amount of dimethyl adipate, hydrazine hydrate and anhydrous methanol in a molar ratio of 1:4:4 and pour them into a flask, react at room temperature for 2 hours, cool and crystallize in an ice water bath, filter and wash with deionized water for 3 times, and dry at 42°C for 3 hours to obtain the self-made adipic acid dihydrazide.

[0038] The preparation steps of homemade 3-hydroxybutenoic acid-2-methylacrylate are as follows: Step 1, weigh 0.5g of hydroquinone and pour it into a flask, stir and heat it to 90°C at a stirring speed of 300r / min, then introduce ethylene oxide gas under nitrogen protection to react for 2h, cool to 60°C after the reaction, and obtain hydroxyethyl methacrylate after reduced pressure distillation; Step 2: Weigh 39 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone into a flask, stir and react under nitrogen protection at a temperature of 5°C, add 25 g of diethylene ketone at a dropping rate of 1 drop / s under stirring conditions of a stirring speed of 300 r / min, then react at a water bath temperature of 50°C for 5 hours, and obtain homemade 3-hydroxybutenoic acid-2-methylacrylate after reduced pressure distillation.

[0039] The alkyl acrylate component is prepared by mixing methyl methacrylate and isooctyl acrylate in an equal weight ratio.

[0040] The acrylic hydrophilic monomer component is prepared by mixing acrylic acid and methacrylic acid in an equal weight ratio.

[0041] The crosslinking monomer component is vinyltrimethoxysilane.

[0042] The emulsifier component is prepared by mixing an anionic emulsifier and a nonionic emulsifier in a weight ratio of 1:5. The anionic emulsifier is sodium salt of fatty alcohol ether vinyl sulfonate, and the nonionic emulsifier is fatty alcohol ethoxylate.

[0043] The initiator component is potassium persulfate; the oxidant component is tert-butyl hydroperoxide; and the reducing agent component is sodium bisulfite.

[0044] The pH regulator component is a sodium hydroxide solution with a mass fraction of 10%; the antifreeze component is glycerol.

[0045] A method for preparing a base film emulsion with formaldehyde removal function, the preparation method comprising: S1, weigh 4 parts by weight of emulsifier component and 80 parts by weight of distilled water into an emulsifying tank, stir at a stirring speed of 300 r / min for 10 min, then add 80 parts by weight of alkyl acrylate component, 3 parts by weight of acrylic acid hydrophilic monomer component, 20 parts by weight of aldehyde-removing functional monomer component, 0.2 parts by weight of cross-linking monomer component and 0.5 parts by weight of initiator component, then stir at the original stirring speed for 30 min, the result is recorded as pre-emulsion; S2, weighing 0.5 parts by weight of the emulsifier component and 60 parts by weight of distilled water into a reactor, stirring at a stirring speed of 500 r / min for 10 min, heating to 70°C and adding 0.1 parts by weight of the initiator component, stirring at the original stirring speed for 10 min, adding 0.05% of the total amount of the pre-emulsion, continuing to stir at the original stirring speed for 10 min, and the resulting mixture is recorded as a seed emulsion; S3, raising the temperature of the seed emulsion to 90°C and then dropping the remaining pre-emulsion, keeping the temperature at the original temperature for 60 minutes after the addition is completed, then cooling to 80°C and dropping 0.3 parts by weight of the oxidant component and 0.3 parts by weight of the reductant component, the result is recorded as the reaction component; S4. Cool the reaction components to 70°C and drop 0.3 parts by weight of the oxidant component and 0.3 parts by weight of the reductant component, cool again to 48°C and drop the pH adjuster component to adjust the pH value to 9, then add 10 parts by weight of the antifreeze component, stir at a stirring speed of 200 r / min for 5 minutes and filter, and the result is a base film emulsion with formaldehyde removal function.

[0046] Comparative Example 1 The base film emulsion with formaldehyde removal function and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that in this comparative example 1, the formaldehyde removal functional monomer component in Example 1 is replaced by the homemade adipic acid dihydrazide in Example 1.

[0047] Comparative Example 2 The base film emulsion with formaldehyde removal function and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that in this comparative example 2, the formaldehyde removal functional monomer component in Example 1 is replaced with the homemade 3-hydroxybutenoic acid-2-methylacrylate in Example 1.

[0048] Performance Testing The base film emulsions with formaldehyde removal function in Examples 1-3 and Comparative Examples 1-2 are marked as Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2, respectively. Then, the performance of Examples 1-3 and Comparative Examples 1-2 is tested. The monomer residual rate of Examples 1-3 and Comparative Examples 1-2 is tested according to the national standard GB / T13985-2009 gas chromatography detection method, and the obtained data is recorded as the residual monomer rate; the formaldehyde purification efficiency of the present invention is tested according to the JCT 1074-2008 standard, and the data is recorded as the formaldehyde purification efficiency; the dry hardness of the film after being applied to the wall of Examples 1-3 and Comparative Examples 1-2 is tested according to the detection method of GB / T 9756-2009, and the obtained data is recorded as the hardness. The obtained data are recorded in the following table:

[0049] The data in the above table show that the formaldehyde purification efficiency of the base film emulsion with formaldehyde removal function in Examples 1-3 is significantly higher than that in Comparative Examples 1-2, indicating that adding the self-made adipic acid dihydrazide and the self-made 3-hydroxybutenoic acid-2-methylacrylate ethylene glycol to the preparation of the base film emulsion with formaldehyde removal function can achieve a better formaldehyde removal effect. In summary, the base film emulsion with formaldehyde removal function prepared in the present invention has an excellent market application prospect.

[0050] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0051] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A base film emulsion with formaldehyde removal function, characterized in that: The base film emulsion with formaldehyde removal function is composed of the following components: distilled water, an alkyl acrylate component, an acrylic hydrophilic monomer component, a formaldehyde removal monomer component, a cross-linking monomer component, an emulsifier component, an initiator component, an oxidant component, a reducing agent component, a pH regulator component and an antifreeze component; The formaldehyde-removing functional monomer component is prepared by mixing self-made adipic acid dihydrazide and self-made 3-hydroxybutenoic acid-2-methylacrylate in an equal weight ratio.

2. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The alkyl acrylate component is at least one of methyl methacrylate, isooctyl acrylate, ethyl acrylate, butyl acrylate, styrene and acrylonitrile.

3. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The acrylic hydrophilic monomer component is at least one of acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl acrylate and hydroxyethyl methacrylate.

4. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The preparation steps of the self-made adipic acid dihydrazide are: Step 1, weighing a calculated amount of adipic acid and anhydrous methanol in a molar ratio of 1:4 and adding them into a flask, then adding a catalyst of potassium hydrogen sulfate with a weight of 6% of adipic acid and heating to reflux, reflux reaction for 1 hour, and then placing it at 68°C for 2 hours, and then collecting the fraction at 110°C / 1.87kPa, and the obtained fraction is recorded as dimethyl adipate; Step 2, weigh the calculated amount of dimethyl adipate, hydrazine hydrate and anhydrous methanol in a molar ratio of 1:4:4 and pour them into a flask, react at room temperature for 2 hours, cool and crystallize in an ice water bath, filter and wash with deionized water for 3 times, and dry at 42°C for 3 hours to obtain the self-made adipic acid dihydrazide.

5. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The preparation steps of the homemade 3-hydroxybutenoic acid-2-methylacrylate are as follows: Step 1, weigh 0.5g of hydroquinone and pour it into a flask, stir and heat it to 90°C at a stirring speed of 300r / min, then introduce ethylene oxide gas under nitrogen protection to react for 2h, cool to 60°C after the reaction, and obtain hydroxyethyl methacrylate after reduced pressure distillation; Step 2: Weigh 39 g of hydroxyethyl methacrylate and 0.5 g of hydroquinone into a flask, stir and react under nitrogen protection at a temperature of 5°C, add 25 g of diethylene ketone at a dropping rate of 1 drop / s under stirring conditions of a stirring speed of 300 r / min, then react at a water bath temperature of 50°C for 5 hours, and obtain homemade 3-hydroxybutenoic acid-2-methylacrylate after reduced pressure distillation.

6. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The crosslinking monomer component is at least one of vinyl trimethoxysilane, vinyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, trimethylolpropane trimethacrylate, allyl methacrylate and divinylbenzene.

7. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The emulsifier component is prepared by mixing an anionic emulsifier and a nonionic emulsifier in a weight ratio of 1-5:1-5, the anionic emulsifier is at least one of isomeric tridecyl alcohol sulfate sodium salt, sodium succinic acid sulfonate, 2-acrylamido-2-methylpropane sulfonate sodium, 3-allyloxy-1-hydroxy-propane phosphate, sodium vinyl sulfonate and fatty alcohol ether vinyl sulfonate sodium salt, and the nonionic emulsifier is at least one of polyoxyethylene sorbitan monooleate, fatty alcohol ethoxylate and alkyl ethoxylate.

8. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The initiator component is at least one of potassium persulfate, ammonium persulfate and sodium persulfate; the oxidant component is at least one of tert-butyl hydroperoxide and hydrogen peroxide; and the reductant component is at least one of sodium bisulfite and vitamin C.

9. The base film emulsion with formaldehyde removal function according to claim 1, characterized in that: The pH regulator component is a sodium hydroxide solution with a mass fraction of 10%; the antifreeze component is at least one of calcium chloride, methanol, ethanol, ethylene glycol, propylene glycol, glycerol and polyethylene glycol.

10. The method for preparing a base film emulsion with formaldehyde removal function according to any one of claims 1 to 9, characterized in that: The preparation method: S1, weigh 0.5-4 parts by weight of emulsifier component and 20-80 parts by weight of distilled water and add them into an emulsifying tank, stir at a stirring speed of 300r / min for 10min, then add 30-80 parts by weight of alkyl acrylate component, 0.5-3 parts by weight of acrylic acid hydrophilic monomer component, 3-20 parts by weight of aldehyde-removing functional monomer component, 0.05-0.2 parts by weight of cross-linking monomer component and 0.1-0.5 parts by weight of initiator component, then stir at the original stirring speed for 15-30min, and the result is recorded as pre-emulsion; S2, weighing 0.5-1 parts by weight of emulsifier component and 60-120 parts by weight of distilled water into a reactor, stirring at a stirring speed of 500r / min for 10min, heating to 70-90°C and adding 0.1-0.5 parts by weight of initiator component, stirring at the original stirring speed for 10min, adding 0.05-15% of the total amount of pre-emulsion, continuing to stir at the original stirring speed for 10-30min, the result is recorded as seed emulsion; S3, raising the temperature of the seed emulsion to 80-90°C and then dropping the remaining pre-emulsion, keeping the temperature at the original temperature for 30-60min after the addition is completed, then cooling to 70-80°C and dropping 0.1-0.3 parts by weight of the oxidant component and 0.1-0.3 parts by weight of the reductant component, the result is recorded as the reaction component; S4. Cool the reaction components to 50-70°C and drop 0.1-0.3 parts by weight of the oxidant component and 0.1-0.3 parts by weight of the reductant component, cool again to 48°C and drop the pH adjuster component to adjust the pH value to 7-9, then add 1-10 parts by weight of the antifreeze component, stir at a stirring speed of 200 r / min for 5 minutes and filter, and the result is a base film emulsion with formaldehyde removal function.

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