CN111117382A - Environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, preparation method thereof and coating - Google Patents
Environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, preparation method thereof and coating Download PDFInfo
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- CN111117382A CN111117382A CN201911399313.8A CN201911399313A CN111117382A CN 111117382 A CN111117382 A CN 111117382A CN 201911399313 A CN201911399313 A CN 201911399313A CN 111117382 A CN111117382 A CN 111117382A
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Abstract
The invention discloses an environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, a preparation method thereof and a coating; the emulsion comprises the following components in parts by weight: 100 parts of deionized water, 30-35 parts of styrene, 40-45 parts of acrylate, 10-15 parts of methacrylate, 1.5-3 parts of alkyl acrylic acid, 1-5 parts of an acrylic acid functional monomer, 0.5-5 parts of an aldehyde-removing functional monomer, 0.1-0.5 part of a functional crosslinking monomer, 1-5 parts of an emulsifier, 0.5-3 parts of an initiator, 0.05-1 part of a buffering agent, 0.1-0.5 part of a residual monomer treatment initiator and 1-4 parts of a rapid aldehyde-removing auxiliary agent; the preparation method is simple in process operation and good in controllability, the emulsion prepared by the preparation method is stable in particle size, good in performance and low in cost, the integration of rapid aldehyde removal and long-term aldehyde removal of an interior wall coating system is realized, and the preparation method has an excellent aldehyde removal effect.
Description
Technical Field
The invention relates to the technical field of environment-friendly coatings and preparation thereof, in particular to an environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, a preparation method thereof and a coating.
Background
With the vigorous development of the domestic house and land industry, the decoration is also made. Most of new materials for interior decoration are organic compound materials, and in a closed indoor environment, organic compounds with different volatility, even the same compound, have different volatilization amounts at different time and have persistence. The interior materials, from wooden doors and windows, furniture such as tables and chairs, and interior wall materials, are adhesives as main finishing and protecting materials, and the adhesives contain a large amount of formaldehyde.
The formaldehyde is an organic matter which is volatile at normal temperature and is also an organic matter which is easy to bring in indoor decoration and affects human health, and the material in the indoor decoration only has the characteristic of continuous volatilization, and is one of indoor pollutants affecting human health for a long time.
The amount of formaldehyde in the air is easy to accumulate in a relatively closed indoor environment, and when the content of the formaldehyde in the air reaches 0.1mg/m3In time, peculiar smell is generated, and the human body feels uncomfortable; up to 0.6mg/m3In time, the human body can be more uncomfortable, and the throat and eyes can feel uncomfortable; the higher the concentration of formaldehyde, the more obvious the discomfort of human body, the body can make corresponding adverse symptoms such as rejection, nausea, vomiting and the like, and even death can be caused seriously.
The existing methods for solving the problem of indoor formaldehyde mainly comprise a ventilation method, a physical adsorption method, a chemical adsorption method and the like. The ventilation method is limited by time in response to the formaldehyde which can be volatilized continuously; the physical adsorption method also has the phenomena of poor effect, reversible adsorption and the like; the chemical adsorption method can effectively solve the problem of volatilizable formaldehyde, and the formaldehyde can be removed through the reaction of the active groups and the aldehyde.
In the field of chemical adsorption, the research and development of acrylic emulsion with formaldehyde absorption function is a widely researched subject of building emulsion, especially interior wall emulsion. This type of emulsion plays an important role in aqueous emulsion systems by copolymerizing functional monomers with which formaldehyde reacts. However, the method has certain limitation, and as a functional monomer, the stability of the system can be affected by too much addition amount, and in a complex coating system, the effect of removing aldehyde can be greatly reduced; and the aldehyde removal effect of the method is better reflected in the drying of the coating film. In a heterogeneous water-based paint system, formaldehyde volatilized from the inner wall coating film in the early stage is much more volatilized from other home decoration products in the later stage, so that the living environment of a user is influenced, and the life safety of construction workers is greatly influenced.
Therefore, a composite emulsion polymerization technology that an emulsion contains a functional auxiliary agent with carbamido as a functional agent for quickly removing aldehyde and a functional monomer capable of generating hydrazone crosslinking with formaldehyde at the middle and later stages as long-acting aldehyde removal is urgently needed, and the problems from construction to aldehyde removal and from aldehyde removal to long-term aldehyde removal are integrally solved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion, the preparation method thereof and the coating, and aims to solve the problem of integration of rapid aldehyde removal and long-term aldehyde removal of interior wall coatings in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in the description of the present invention, it is to be understood that "a plurality" means two or more unless otherwise specified.
An environment-friendly internal wall aldehyde-removing styrene-acrylic emulsion contains a functional auxiliary agent with carbamido as a composite aldehyde-removing emulsion for quickly removing aldehyde and polymerizing a functional monomer capable of absorbing formaldehyde as long-acting aldehyde-removing styrene acrylate copolymerization, and comprises the following components in parts by weight: 100 parts of deionized water, 30-35 parts of styrene, 40-45 parts of acrylate, 10-15 parts of methacrylate, 1.5-3 parts of alkyl acrylic acid, 1-5 parts of acrylic acid functional monomer, 0.5-5 parts of aldehyde-removing functional monomer, 0.1-0.5 part of functional crosslinking monomer, 1-5 parts of emulsifier, 0.5-3 parts of initiator, 0.05-1 part of buffering agent, 0.1-0.5 part of residual monomer treatment initiator and 1-4 parts of rapid aldehyde-removing auxiliary agent.
In the emulsion, the rapid aldehyde removal auxiliary agent is 2-imidazolidinone, has good water solubility and strong stability in a system, and the 2-imidazolidinone reacts with formaldehyde to generate 1- (hydroxymethyl) imidazolidin-2-one, so that the emulsion is an aldehyde removal reaction, has a formaldehyde capturing effect and is a formaldehyde capturing agent commonly used in paint.
The long-acting aldehyde removal of the emulsion is realized by crosslinking alkyl acrylic acid polymerized in a molecular chain with an aldehyde removal functional monomer, and absorbing formaldehyde in air by the aldehyde removal functional monomer which does not react with the formaldehyde in the long-term drying process of a coating film and after the coating film is dried, so that the effect of long-acting aldehyde removal is achieved.
Specifically, the acrylate is one or more of butyl acrylate, ethyl acrylate, methyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate.
Specifically, the methacrylate comprises one or more of methyl methacrylate, butyl methacrylate, amyl methacrylate and isooctyl methacrylate.
Specifically, the alkyl acrylic acid comprises one or more of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the acrylic acid functional monomer comprises one or more of acrylamide, N-hydroxy acrylamide, diacetone acrylamide, glycidyl methacrylate and tert-butyl acrylate. Preferably, the alkyl acrylic acid is diacetone acrylamide; the diacetone acrylamide has good solubility in acrylic monomers and styrene monomers, has excellent aldehyde removal performance when being used in combination with an aldehyde removal functional monomer adipic dihydrazide to play a crosslinking role in the polymerization reaction of emulsion, and can ensure that a paint film is not easy to crack and has good glossiness.
Specifically, the aldehyde-removing functional monomer comprises one or more of 2-imidazolidinone, 1, 3-dimethyl-2-imidazolidinone, ethanolamine, thiourea and adipic acid dihydrazide. Preferably, the aldehyde-removing functional monomer is adipic acid dihydrazide; when the adipic acid dihydrazide and the diacetone acrylamide are used in a matching way, the crosslinking effect is realized in the polymerization reaction of the emulsion, and the excellent aldehyde removal performance is realized.
Specifically, the functional crosslinking monomer comprises one or more of phosphate ester monomer, vinyl trimethoxy silane and vinyl triethoxy silane.
Specifically, the emulsifier comprises an anionic emulsifier and a nonionic emulsifier in a mass ratio of 1-10: 1-5. The anionic emulsifier and the nonionic emulsifier are matched for use, so that a synergistic effect can be generated, and the emulsifying effect is enhanced; the emulsifying agent in the proportion enables the emulsion to be smoothly emulsified and has good controllability. More specifically, the anionic emulsifier comprises one or more of allyl aliphatic polyoxyethylene sodium sulfate, sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl naphthalene sulfonate, and sodium alkyl naphthalene sulfonate. The non-ion is one or a mixture of more of alkyl polyoxyethylene ether, fluorine-containing polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.
Specifically, the initiator comprises one or a mixture of more of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and sodium hypophosphite; the residual monomer processing initiator comprises one or more of tert-butyl hydroperoxide, tert-butyl peroxybenzoate, sodium bisulfite and ascorbic acid.
The buffer is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and sodium acetate.
The preparation method of the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion comprises the following steps:
step S001, preparing a bottom material a: adding 35-45 parts of deionized water, a buffering agent and 0.5-3 parts of an emulsifying agent into a reaction kettle with a condenser, a variable speed stirrer, a thermometer and a constant flow dropping pump device, wherein the deionized water is used for washing the emulsifying agent into the reaction kettle completely, and the emulsifying agent can not be remained and is stirred uniformly;
step S002, preparation of monomer pre-emulsion b: adding 30-40 parts of deionized water and the rest of emulsifier into a dispersing and stirring container with a fume hood at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, an acrylic acid functional monomer, a functional crosslinking monomer and an aldehyde-removing functional monomer, mixing to obtain a uniform emulsion, and stirring for 30min for later use;
step S003. preparation of initiator solution c: dissolving 0.3-2.5 parts of initiator into 3-5 parts of deionized water, and stirring and dissolving for later use;
step S004. preparation of an initiator solution d: dissolving 0.2-1 part of initiator into 15-20 parts of deionized water, and stirring and dissolving for later use;
step S005, preparation of the residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 3-5 parts of deionized water, and stirring and dissolving for later use;
step S006, preparing a rapid aldehyde removal auxiliary agent solution f: dissolving the rapid aldehyde removal auxiliary agent into 1-5 parts of deionized water, and stirring and dissolving for later use;
step S007, when the temperature of the reaction kettle in the step S001 rises to 82-84 ℃, adding an initiator solution c and 5% -10% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d after reacting for 15-30 min, controlling the dropwise adding time to be 190-270 min, and finishing dropwise adding the monomer pre-emulsion b 5-10 min earlier than the initiator solution d;
s008, heating the reaction kettle to 86-88 ℃, preserving heat for 60-90 min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, treating the residual monomer, dropwise adding for 30-60 min, continuously curing for 15-30 min, continuously cooling to below 45 ℃, adjusting the pH to 7-9, adding the rapid formaldehyde removal auxiliary agent solution f, dispersedly stirring for 10-30 min, and filtering to obtain the styrene-acrylic emulsion.
An environment-friendly interior wall aldehyde-removing water-based paint comprises the environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion.
Has the advantages that:
the invention provides an environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, a preparation method thereof and a coating, and the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion has the following advantages:
1. the emulsion can realize the effects of removing aldehyde from paint preparation to construction, and from survival to long-term removal of the aldehyde in the interior wall coating product. Under the condition of normal temperature, the functional auxiliary agent with carbamido is used for quickly removing aldehyde, and formaldehyde in the emulsion and the interior wall coating auxiliary agent is subjected to aldehyde removal reaction, so that the formaldehyde is prevented from generating harm to construction workers in the processes of paint preparation, tank opening and construction; and the aldehyde-removing functional monomer generates relatively stable hydrazone linking reaction after the paint film is semi-dried or even dried, so that the formaldehyde in the air can be captured, the effect of continuously purifying the formaldehyde is achieved, and the indoor harm of the formaldehyde is reduced to the lowest level.
2. The aldehyde-removing functional monomer and the rapid aldehyde-removing auxiliary agent are polar materials, have a normal-temperature crosslinking effect in the drying process of the emulsion, and cannot generate negative influence on the basic performance of the product.
3. The emulsion takes styrene acrylate as a main monomer, so that good hardness and scrub resistance of the product can be provided, and basic performance of the product is improved by the cross-linking functional monomer.
4. The emulsion utilizes the reasonable collocation and the synergistic effect of the charge stability of the anionic emulsifier and the steric hindrance characteristic of the nonionic emulsifier to improve the stability of latex ions; the using amount of the emulsifier avoids the defects of poor water resistance, poor compactness and other paint films caused by excessive emulsifier.
5. The preparation method of the emulsion has simple process operation, adopts a pre-emulsification semi-continuous automatic dripping process, has stable product particle size, narrow particle size distribution, good performance and low cost, and is beneficial to realizing large-scale industrial production.
Detailed Description
The invention provides an environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion, a preparation method thereof and a coating, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail by the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
An environment-friendly internal wall aldehyde-removing styrene-acrylic emulsion contains a functional auxiliary agent with carbamido as a composite aldehyde-removing emulsion for quickly removing aldehyde and polymerizing a functional monomer capable of absorbing formaldehyde as long-acting aldehyde-removing styrene acrylate copolymerization, and comprises the following components in parts by weight: 100 parts of deionized water, 35 parts of styrene, 45 parts of acrylate, 13 parts of methacrylate, 1.5 parts of alkyl acrylic acid, 3.5 parts of acrylic acid functional monomer, 2 parts of aldehyde-removing functional monomer, 0.1 part of functional crosslinking monomer, 1 part of emulsifier, 0.5 part of initiator, 1 part of buffering agent, 0.5 part of residual monomer treatment initiator and 1 part of rapid aldehyde-removing auxiliary agent.
The acrylate is butyl acrylate, ethyl acrylate or 2-ethylhexyl acrylate.
The methacrylate is methyl methacrylate, butyl methacrylate or isooctyl methacrylate.
The alkyl acrylic acid crosslinking monomer is acrylic acid and itaconic acid.
The acrylic acid functional monomer is diacetone acrylamide and tert-butyl acrylate.
The aldehyde-removing functional auxiliary agent is 2-imidazolidinone and 1, 3-dimethyl-2-imidazolidinone.
The functional crosslinking monomer is phosphate ester monomer.
The emulsifier is an anionic emulsifier and a nonionic emulsifier in a mass ratio of 1: 5, the anionic emulsifier is sodium alkyl benzene sulfonate and sodium alkyl naphthalene sulfonate, and the nonionic emulsifier is alkyl polyoxyethylene ether.
The initiator is sodium persulfate.
The residual monomer treatment initiator is tert-butyl hydroperoxide.
The buffer is sodium carbonate.
The preparation method of the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion comprises the following steps:
preparation of a backing material a: adding 40 parts of deionized water, a buffering agent and 0.5 part of an emulsifying agent into a reaction kettle with a condenser, a variable speed stirrer, a thermometer and a constant flow dropping pump device, washing the emulsifying agent into the reaction kettle by the deionized water, and uniformly stirring the mixture, wherein the emulsifying agent cannot remain;
preparation of monomer pre-emulsion b: adding 32 parts of deionized water and the rest of emulsifier into a dispersing and stirring container with a fume hood at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, acrylic acid functional monomer, functional crosslinking monomer and aldehyde-removing functional monomer, mixing to obtain uniform emulsion, and stirring for 30min for later use;
preparation of initiator solution c: dissolving 0.3 part of initiator into 5 parts of deionized water, and stirring and dissolving for later use;
preparation of initiator solution d: dissolving 0.2 part of initiator into 16 parts of deionized water, and stirring and dissolving for later use;
preparation of residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 3 parts of deionized water, and stirring and dissolving for later use;
preparing a rapid aldehyde removal auxiliary solution f: dissolving the rapid aldehyde removal auxiliary agent into 4 parts of deionized water, and stirring and dissolving for later use;
when the temperature of the reaction kettle is raised to 82-84 ℃, adding an initiator solution c and 5% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, reacting for 15min, simultaneously dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d, controlling the dropwise adding time to be 200min, and enabling the monomer pre-emulsion b to be 5min earlier than the initiator solution d;
heating the reaction kettle to 86-88 ℃, keeping the temperature for 60min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, treating the residual monomer, dropwise adding for 40min, continuously curing for 20min, continuously cooling to below 45 ℃, adjusting the pH to 7.5, adding the rapid aldehyde removal auxiliary agent solution f, dispersing and stirring for 15min, and filtering to obtain the styrene-acrylic emulsion.
Example 2
An environment-friendly internal wall aldehyde-removing styrene-acrylic emulsion contains a functional auxiliary agent with carbamido as a composite aldehyde-removing emulsion for quickly removing aldehyde and polymerizing a functional monomer capable of absorbing formaldehyde as long-acting aldehyde-removing styrene acrylate copolymerization, and comprises the following components in parts by weight: 100 parts of deionized water, 33 parts of styrene, 44 parts of acrylate, 15 parts of methacrylate, 2.5 parts of alkyl acrylic acid, 4.5 parts of acrylic acid functional monomer, 0.5 part of aldehyde-removing functional monomer, 0.2 part of functional crosslinking monomer, 5 parts of emulsifier, 1 part of initiator, 0.05 part of buffering agent, 0.2 part of residual monomer treatment initiator and 2 parts of rapid aldehyde-removing auxiliary agent.
The acrylate is ethyl acrylate or methyl acrylate.
The methacrylate is butyl methacrylate, amyl methacrylate and isooctyl methacrylate.
The alkyl acrylic acid crosslinking monomer is acrylic acid and methacrylic acid.
The acrylic acid functional monomer is acrylamide and tert-butyl acrylate.
The aldehyde-removing functional additive is thiourea and adipic acid dihydrazide.
The functional crosslinking monomer is vinyl trimethoxy silane.
The emulsifier is an anionic emulsifier and a nonionic emulsifier in a mass ratio of 2: 1, and the anionic emulsifier is allyl aliphatic polyoxyethylene sodium sulfate and sodium alkyl benzene sulfonate; the nonionic emulsifier is alkyl polyoxyethylene ether or isomeric alcohol polyoxyethylene ether.
The initiator is sodium hypophosphite or ammonium persulfate.
The residual monomer treatment initiator is sodium bisulfite.
The buffer is sodium carbonate.
The preparation method of the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion comprises the following steps:
preparation of a backing material a: adding 35 parts of deionized water, a buffering agent and 2.5 parts of an emulsifying agent into a reaction kettle with a condenser, a variable speed stirrer, a thermometer and a constant flow dropping pump device, completely washing the emulsifying agent into the reaction kettle by using the deionized water, and uniformly stirring the mixture, wherein the emulsifying agent cannot remain;
preparation of monomer pre-emulsion b: adding 40 parts of deionized water and the rest of emulsifier into a dispersing and stirring container with a fume hood at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, acrylic acid functional monomer, functional crosslinking monomer and aldehyde-removing functional monomer, mixing to obtain uniform emulsion, and stirring for 30min for later use;
preparation of initiator solution c: dissolving 0.6 part of initiator into 4 parts of deionized water, and stirring and dissolving for later use;
preparation of initiator solution d: dissolving 0.4 part of initiator into 17 parts of deionized water, and stirring and dissolving for later use;
preparation of residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 3 parts of deionized water, and stirring and dissolving for later use;
preparing a rapid aldehyde removal auxiliary solution f: dissolving the rapid aldehyde-removing auxiliary agent into 1 part of deionized water, and stirring and dissolving for later use;
when the temperature of the reaction kettle is raised to 82-84 ℃, adding an initiator solution c and 10% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, reacting for 30min, and then simultaneously dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d, wherein the dropwise adding time is controlled to be 190min, and the dropwise adding of the monomer pre-emulsion b is finished 8min earlier than that of the initiator solution d;
heating the reaction kettle to 86-88 ℃, keeping the temperature for 60min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, treating the residual monomer, dropwise adding for 30min, continuously curing for 20min, continuously cooling to below 45 ℃, adjusting the pH to 7, adding the rapid aldehyde removal auxiliary agent solution f, dispersing and stirring for 15min, and filtering to obtain the styrene-acrylic emulsion.
Example 3
An environment-friendly internal wall aldehyde-removing styrene-acrylic emulsion contains a functional auxiliary agent with carbamido as a composite aldehyde-removing emulsion for quickly removing aldehyde and polymerizing a functional monomer capable of absorbing formaldehyde as long-acting aldehyde-removing styrene acrylate copolymerization, and comprises the following components in parts by weight: 100 parts of deionized water, 30 parts of styrene, 42 parts of acrylate, 10 parts of methacrylate, 2 parts of alkyl acrylic acid, 1 part of acrylic acid functional monomer, 5 parts of aldehyde-removing functional monomer, 0.3 part of functional crosslinking monomer, 4 parts of emulsifier, 3 parts of initiator, 0.3 part of buffer, 0.1 part of residual monomer treatment initiator and 3 parts of rapid aldehyde-removing assistant.
The acrylate is methyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate.
The methacrylate is butyl methacrylate, amyl methacrylate and isooctyl methacrylate.
The alkyl acrylic acid crosslinking monomer is methacrylic acid and maleic acid.
The acrylic acid functional monomer is N-hydroxy acrylamide and glycidyl methacrylate.
The aldehyde-removing functional auxiliary agent is 2-imidazolidinone and ethanolamine.
The functional crosslinking monomer is vinyl trimethoxy silane.
The emulsifier is an anionic emulsifier and a nonionic emulsifier in a mass ratio of 3: 2, the anionic emulsifier is sodium alkyl naphthalene sulfonate sulfate, and the nonionic emulsifier is fluorine-containing polyoxyethylene ether.
The initiator is hydrogen peroxide.
The residual monomer treatment initiator is tert-butyl peroxybenzoate and sodium bisulfite.
The buffer is ammonium carbonate.
The preparation method of the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion comprises the following steps:
preparation of a backing material a: adding 45 parts of deionized water, a buffering agent and 3 parts of an emulsifying agent into a reaction kettle with a condenser, a variable speed stirrer, a thermometer and a constant flow dropping pump device, completely washing the emulsifying agent into the reaction kettle by using the deionized water, and uniformly stirring the mixture, wherein the emulsifying agent cannot remain;
preparation of monomer pre-emulsion b: adding 30 parts of deionized water and the rest of emulsifier into a dispersing and stirring container with a fume hood at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, acrylic acid functional monomer, functional crosslinking monomer and aldehyde-removing functional monomer, mixing to obtain uniform emulsion, and stirring for 30min for later use;
preparation of initiator solution c: dissolving 2 parts of initiator into 3 parts of deionized water, and stirring and dissolving for later use;
preparation of initiator solution d: dissolving 1 part of initiator into 15 parts of deionized water, and stirring and dissolving for later use;
preparation of residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 4 parts of deionized water, and stirring and dissolving for later use;
preparing a rapid aldehyde removal auxiliary solution f: dissolving the rapid aldehyde removal auxiliary agent into 3 parts of deionized water, and stirring and dissolving for later use;
when the temperature of the reaction kettle is raised to 82-84 ℃, adding an initiator solution c and 7% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, reacting for 20min, and then simultaneously dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d, wherein the dropwise adding time is controlled to be 250min, and the dropwise adding of the monomer pre-emulsion b is finished 10min earlier than that of the initiator solution d;
heating the reaction kettle to 86-88 ℃, keeping the temperature for 70min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, treating the residual monomer, dropwise adding for 45min, continuously curing for 25min, continuously cooling to below 45 ℃, adjusting the pH to 8.5, adding the rapid aldehyde removal auxiliary agent solution f, dispersing and stirring for 25min, and filtering to obtain the styrene-acrylic emulsion.
Example 4
An environment-friendly internal wall aldehyde-removing styrene-acrylic emulsion contains a functional auxiliary agent with carbamido as a composite aldehyde-removing emulsion for quickly removing aldehyde and polymerizing a functional monomer capable of absorbing formaldehyde as long-acting aldehyde-removing styrene acrylate copolymerization, and comprises the following components in parts by weight: 100 parts of deionized water, 31 parts of styrene, 40 parts of acrylic ester, 11 parts of methacrylic ester, 3 parts of alkyl acrylic acid, 2 parts of acrylic acid functional monomer, 4 parts of aldehyde-removing functional monomer, 0.5 part of functional crosslinking monomer, 3 parts of emulsifier, 2 parts of initiator, 0.2 part of buffer, 0.3 part of residual monomer treatment initiator and 4 parts of rapid aldehyde-removing assistant.
The acrylate is butyl acrylate, ethyl acrylate and methyl acrylate.
The methacrylate is methyl methacrylate and isooctyl methacrylate.
The alkyl acrylic acid crosslinking monomer is acrylic acid and itaconic acid.
The acrylic acid functional monomer is acrylamide and diacetone acrylamide.
The aldehyde-removing functional auxiliary agent is adipic acid dihydrazide.
The functional crosslinking monomer is vinyl trimethoxy silane and vinyl triethoxy silane.
The emulsifier is an anionic emulsifier and a nonionic emulsifier in a mass ratio of 5: 2, the anionic emulsifier is sodium alkyl sulfate and sodium allyl aliphatic polyoxyethylene sulfate, and the nonionic emulsifier is alkyl polyoxyethylene ether.
The initiator is sodium persulfate and potassium persulfate.
The residual monomer processing initiator is ascorbic acid.
The buffer is sodium bicarbonate.
The preparation method of the environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion comprises the following steps:
preparation of a backing material a: adding 38 parts of deionized water, a buffering agent and 2 parts of an emulsifying agent into a reaction kettle with a condenser, a variable speed stirrer, a thermometer and a constant flow dropping pump device, completely washing the emulsifying agent into the reaction kettle by using the deionized water, and uniformly stirring the mixture, wherein the emulsifying agent cannot remain;
preparation of monomer pre-emulsion b: adding 34 parts of deionized water and the rest of emulsifier into a dispersing and stirring container with a fume hood at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, acrylic acid functional monomer, functional crosslinking monomer and aldehyde-removing functional monomer, mixing to obtain uniform emulsion, and stirring for 30min for later use;
preparation of initiator solution c: dissolving 1.2 parts of initiator into 4 parts of deionized water, and stirring and dissolving for later use;
preparation of initiator solution d: dissolving 0.8 part of initiator into 15 parts of deionized water, and stirring and dissolving for later use;
preparation of residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 4 parts of deionized water, and stirring and dissolving for later use;
preparing a rapid aldehyde removal auxiliary solution f: dissolving the rapid aldehyde-removing auxiliary agent into 5 parts of deionized water, and stirring and dissolving for later use;
when the temperature of the reaction kettle is raised to 82-84 ℃, adding an initiator solution c and 8% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, reacting for 20min, and then simultaneously dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d, wherein the dropwise adding time is controlled to be 220min, and the dropwise adding of the monomer pre-emulsion b is finished 10min earlier than that of the initiator solution d;
heating the reaction kettle to 86-88 ℃, keeping the temperature for 90min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, treating the residual monomer, dropwise adding for 50min, continuously curing for 30min, continuously cooling to below 45 ℃, adjusting the pH to 8, adding the rapid aldehyde removal auxiliary agent solution f, dispersing and stirring for 25min, and filtering to obtain the styrene-acrylic emulsion.
The emulsions prepared in examples 1 to 4 were tested for aldehyde removal efficiency, coating film hardness, scrub resistance, water resistance and denseness, respectively, and the results are shown in Table 1.
TABLE 1 Performance parameters of emulsions prepared in examples 1-4
As can be seen from Table 1, the aldehyde-removing styrene-acrylic emulsion of the invention has excellent aldehyde-removing efficiency in the early stage and long-term aldehyde-removing efficiency, and has good scrubbing resistance.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (10)
1. The environment-friendly interior wall formaldehyde-removing styrene-acrylic emulsion is characterized by comprising the following components in parts by weight: 100 parts of deionized water, 30-35 parts of styrene, 40-45 parts of acrylate, 10-15 parts of methacrylate, 1.5-3 parts of alkyl acrylic acid, 1-5 parts of acrylic acid functional monomer, 0.5-5 parts of aldehyde-removing functional monomer, 0.1-0.5 part of functional crosslinking monomer, 1-5 parts of emulsifier, 0.5-3 parts of initiator, 0.05-1 part of buffering agent, 0.1-0.5 part of residual monomer treatment initiator and 1-4 parts of rapid aldehyde-removing auxiliary agent.
2. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as claimed in claim 1, wherein the acrylate is one or more of butyl acrylate, ethyl acrylate, methyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate.
3. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as claimed in claim 1, wherein the methacrylate comprises one or more of methyl methacrylate, butyl methacrylate, amyl methacrylate and isooctyl methacrylate.
4. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion according to claim 1, wherein the alkyl acrylic acid comprises one or more of acrylic acid, methacrylic acid, itaconic acid and maleic acid, and the acrylic functional monomer comprises one or more of acrylamide, N-hydroxy acrylamide, diacetone acrylamide, glycidyl methacrylate and tert-butyl acrylate.
5. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion according to claim 1, wherein the aldehyde-removing functional monomer comprises one or more of 2-imidazolidinone, 1, 3-dimethyl-2-imidazolidinone, ethanolamine, thiourea and adipic acid dihydrazide.
6. The environment-friendly interior wall aldehyde and benzene removing emulsion as claimed in claim 1, wherein the functional crosslinking monomer comprises one or more of phosphate ester monomer, vinyl trimethoxy silane and vinyl triethoxy silane.
7. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as claimed in claim 1, wherein the emulsifier comprises an anionic emulsifier and a nonionic emulsifier in a mass ratio of 1-10: 1-5.
8. The environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as defined in claim 1, wherein the initiator comprises one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and sodium hypophosphite; the residual monomer processing initiator comprises one or more of tert-butyl hydroperoxide, tert-butyl peroxybenzoate, sodium bisulfite and ascorbic acid.
9. The preparation method of the environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as defined in any one of claims 1 to 8, which comprises the following steps:
step S001, preparing a bottom material a: adding 35-45 parts of deionized water, a buffering agent and 0.5-3 parts of an emulsifying agent into a reaction kettle, and uniformly stirring;
step S002, preparation of monomer pre-emulsion b: adding 30-40 parts of deionized water and the rest of emulsifier into a dispersing and stirring container at normal temperature and normal pressure, uniformly dispersing, adding styrene, acrylate, methacrylate, alkyl acrylic acid, an acrylic acid functional monomer, a functional crosslinking monomer and an aldehyde-removing functional monomer, mixing to obtain a uniform emulsion, and stirring for 30min for later use;
step S003. preparation of initiator solution c: dissolving 0.3-2.5 parts of initiator into 3-5 parts of deionized water, and stirring and dissolving for later use;
step S004. preparation of an initiator solution d: dissolving 0.2-1 part of initiator into 15-20 parts of deionized water, and stirring and dissolving for later use;
step S005, preparation of the residual monomer treatment initiator solution e: dissolving the residual monomer treatment initiator into 3-5 parts of deionized water, and stirring and dissolving for later use;
step S006, preparing a rapid aldehyde removal auxiliary agent solution f: dissolving the rapid aldehyde removal auxiliary agent into 1-5 parts of deionized water, and stirring and dissolving for later use;
step S007, when the temperature of the reaction kettle in the step S001 rises to 82-84 ℃, adding an initiator solution c and 5% -10% of a monomer pre-emulsion b, starting timing when the temperature rises to 82 ℃, dropwise adding the rest of the monomer pre-emulsion b and the initiator solution d after reacting for 15-30 min, controlling the dropwise adding time to be 190-270 min, and finishing dropwise adding the monomer pre-emulsion b 5-10 min earlier than the initiator solution d;
s008, heating the reaction kettle to 86-88 ℃, preserving heat for 60-90 min, cooling to 70-75 ℃, dropwise adding the residual monomer treatment initiator solution e, dropwise adding for 30-60 min, continuously curing for 15-30 min, continuously cooling to below 45 ℃, adjusting the pH to 7-9, adding the rapid aldehyde removal auxiliary agent solution f, dispersedly stirring for 10-30 min, and filtering to obtain the styrene-acrylic emulsion.
10. An environment-friendly interior wall aldehyde-removing water-based paint, which is characterized by comprising the environment-friendly interior wall aldehyde-removing styrene-acrylic emulsion as defined in any one of claims 1-8.
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