CN110724416A - Preparation method of modified hydroxyl ester-based polymer emulsion - Google Patents

Preparation method of modified hydroxyl ester-based polymer emulsion Download PDF

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CN110724416A
CN110724416A CN201910911564.3A CN201910911564A CN110724416A CN 110724416 A CN110724416 A CN 110724416A CN 201910911564 A CN201910911564 A CN 201910911564A CN 110724416 A CN110724416 A CN 110724416A
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based polymer
initiator
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polymer emulsion
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王迎斌
刘飞宏
贺行洋
苏英
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Hubei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/06—Copolymers of allyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/08—Allyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a preparation method of modified hydroxyl ester-based polymer emulsion. The required raw materials comprise: 1.0-4.2 parts of hydrophilic small monomer for emulsification, 1.7-4.5 parts of hydrophobic small monomer for emulsification, 18-51 parts of hydroxyl small monomer, 0.05-0.26 part of emulsion initiator, 2.2-5.4 parts of initiator a, 3.5-6.6 parts of initiator b, 450 parts of ester-based small monomer 380 ion-doped material, 6.2-9.3 parts of cross-linking agent, 0.06-0.28 part of chain transfer agent, 0.5-1.0 part of graphene oxide, 15-40 parts of polyether, 5-10 parts of neutralizing agent, 5-10 parts of pH regulator, 2.0-6.5 parts of auxiliary emulsifying agent, 0.4-1.3 parts of liquid film reinforcing agent and the balance of water, wherein the total mass part is 1000 and the solid content is 50%. The waterproof coating is suitable for being mixed with cement, a large number of hydroxyl groups can stably complex calcium ions, hydrolysis of the calcium ions is effectively inhibited, the strength of the cement is improved, the waterproof effect is enhanced, the internal bonding force of a polymer can be enhanced through the hydrogen bonds in the hydroxyl molecules, the adhesive force between the polymer and a matrix is enhanced through the strong hydrophilic effect, and the tensile strength of the formed polymer emulsion is obviously enhanced through the addition of the graphene oxide; the water resistance is also improved to a certain extent.

Description

Preparation method of modified hydroxyl ester-based polymer emulsion
Technical Field
The invention belongs to the technical field of building waterproof materials, and particularly relates to a preparation method of modified hydroxyl ester-based polymer emulsion.
Background
The waterproof coating is simple in construction, high in coating film strength and good in waterproof effect, and is widely applied to building waterproof materials.
The waterproof market can be divided into three parts of a tool, home decoration and leakage repair, the tool waterproof refers to waterproof design and construction applied to large-scale building engineering, and the using amount is large; the home decoration waterproofing refers to small-scale waterproofing construction of home decoration such as commercial houses, private buildings and the like, and the scale is small but the quantity is remarkable; the leakage repairing refers to a repairing measure which is taken for the leakage of the building which is not subjected to the waterproof operation after or before the waterproof warranty period. The waterproof coating can be suitable for various markets and has wide use.
The patent CN106189635A discloses a waterproof paint, and the invention discloses a waterproof paint which is composed of the following components in parts by weight: 35-45 parts of poly diacetone acrylamide, 12-20 parts of epoxy resin, 0.3-0.5 part of coupling agent, 0.5-2 parts of flatting agent, 0.1-0.5 part of defoaming agent and 2-6 parts of curing agent. The invention has the following advantages: after the coating is formed into a film, the coating has a soft visual effect with low light, good adherence, cold and hot hardness and corrosion resistance, and good adherence with a finish coat containing fluoropolymer.
The patent CN108384350A discloses a waterproof special coating, and the invention provides a waterproof special coating, which is composed of the following raw materials in parts by weight: 15-25 parts of cement, 2-4 parts of calcium carbonate, 6-12 parts of titanium dioxide, 7-13 parts of quartz sand, 22-32 parts of acrylic elastic emulsion, 4-8 parts of nano silicon oxide, 8-14 parts of anti-aging agent, 1-3 parts of wetting agent, 2-6 parts of dispersing agent, 16-20 parts of styrene-acrylic emulsion, 4-10 parts of defoaming agent, 5-11 parts of polyvinyl alcohol, 5-9 parts of antioxidant, 3-7 parts of heavy calcium carbonate, 2-4 parts of silane coupling agent, 6-10 parts of polyethylene glycol and 10-18 parts of water. The invention has good adhesion, good compactness, difficult falling, safety and environmental protection, and excellent elasticity of waterproofness, sun protection and freezing resistance, and meets various market requirements.
The patent CN104356614A discloses a preparation method of PET polyester based on an emulsion polymerization method, relates to a preparation method of PET polyester based on an emulsion polymerization method, and belongs to the technical field of high polymer materials. The method comprises the following steps: adding water and an emulsifier into a reactor, stirring uniformly, adding acrylic acid, hydroxyethyl acrylate and methyl methacrylate, stirring uniformly, adding an initiator, heating for polymerization, adding ferric trioxide, glass fiber and silicon oxide powder, stirring uniformly, performing suction filtration to obtain a polymer, washing a filter cake with ethanol, and drying the filter cake to obtain a prepolymer; uniformly mixing the prepolymer, polyethylene glycol terephthalate, butanediol diacrylate, a nucleating agent, an antioxidant, a silane coupling agent and a lubricant to obtain a mixture; and (3) feeding the mixture into a double-screw extruder for extrusion and granulation.
The existing waterproof coating of the waterproof coating has the problems of unbalanced performances in other aspects such as adhesive force, internal binding force, tensile strength and the like while ensuring better waterproof performance, and a coating product with balanced comprehensive performance and better waterproof performance is urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a modified hydroxyl ester-based polymer waterproof coating.
The invention prepares a macromolecular material containing hydroxyl ester groups by a super-concentrated emulsion method. The polymer is formed by polymerizing hydrophilic and hydrophobic small monomers through a super-concentrated emulsion, the used ingredients are hydroxyl hydrophilic small monomers and ester hydrophobic small monomers, an initiator and a cross-linking agent are added, the initiator provides reaction conditions for the two small monomers, the cross-linking agent provides cohesiveness for a finished product, and the hydrophobic small monomers fully wrap the hydrophilic small monomers by utilizing the property of the super-concentrated emulsion to carry out polymerization reaction with high efficiency, so that the prepared polymer meets the requirement of the required molecular weight, and the reaction degree can be well controlled to adjust the molecular weight. The waterproof coating has the advantages of the traditional waterproof coating, and has better ductility, tensile resistance and waterproofness than the traditional waterproof coating, and long service life.
The technical scheme provided by the invention is as follows:
a preparation method of modified hydroxyl ester-based polymer emulsion comprises the following steps:
1) directly adding 4.0-6.0 parts of water, 1.0-4.2 parts of hydrophilic small monomer for emulsification, 1.7-4.5 parts of hydrophobic small monomer for emulsification, 0.05-0.26 part of emulsion initiator and 0.06-0.28 part of chain transfer agent into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 70-90 ℃ for 1-2 hours, preserving heat for 1-2 hours, and cooling to obtain the super-concentrated emulsifier;
the hydrophilic small monomer for emulsification is one or more of allyl alcohol, methyl allyl alcohol and isoamylol alcohol; preferably one or two of allyl alcohol and isopentenol; more preferably a composition of propenol and prenol in a mass ratio of 1: 1.
The hydrophobic small monomers for emulsification are one or more of ester hydrophobic monomers (methyl) n-butyl acrylate, isobutyl (methyl) acrylate, lauryl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, octadecyl (methyl) acrylate and benzyl methacrylate; preferably one or two of isobutyl (meth) acrylate, lauryl (meth) acrylate and 2-ethylhexyl (meth) acrylate; more preferably a composition of lauryl (meth) acrylate and 2-ethylhexyl (meth) acrylate in a mass ratio of 1: 3.
2) Adding 18-51 parts of hydroxyl hydrophilic small monomer, 380-450 parts of ester hydrophobic small monomer, 6.2-9.3 parts of cross-linking agent, 15-40 parts of polyether and 0.5-1.0 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5-10 parts of pH regulator to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction mixed monomer;
the hydroxyl hydrophilic small monomer is one or more of allyl alcohol, methyl allyl alcohol, isopentenol and 4- (ethyleneoxy) -1-butanol; preferably one or two of methyl allyl alcohol and isoamylol alcohol; more preferably a composition of methacrylic alcohol and prenol in a mass ratio of 1: 2;
the ester hydrophobic small monomer is one or more of 2-phenoxyethyl methacrylate, 2-propylheptyl acrylate, methacryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl ester and methacryloyloxyethyl hexahydrophthalate monoester; preferably one or more of methacryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl ester and methacryloyloxyethyl hexahydrophthalate monoester; more preferably a composition of methacryloyloxyethyl phthalate monoester and 2-methacryloyloxyethyl ester in a mass ratio of 2: 1;
3) adding 5-16 parts of deionized water, 6.81-15.24 parts of prepared super-concentrated emulsifier, 2.0-6.5 parts of co-emulsifier and 0.4-1.3 parts of liquid film reinforcing agent into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 1-3 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump, dropwise adding for 1.5-2 hours, and continuously stirring for 10-20 minutes after dropwise adding is finished to prepare super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 2-4 minutes at the speed of 900-;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a water bath at 65-80 ℃ for 6-8 hours at constant temperature, firstly dripping the solution A for 5-7 hours, and then dripping the solution B for 1-2 hours, wherein the solution A comprises 50 parts of water and 2.2-5.4 parts of initiator a, and the solution B comprises 50 parts of water and 3.5-6.6 parts of initiator B;
7) after the reaction is finished, preserving heat, curing for 1-2 hours, cooling, adding 5-10 parts of neutralizing agent, and supplementing water until the total solution mass is 1000 parts.
Specifically, the coemulsifier is one or more of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate. Preferably one or more of stearyl methacrylate, hexadecane and hexadecanol; more preferably a combination of stearyl methacrylate and hexadecane in a mass ratio of 3: 4.
In particular, the method comprises the following steps of,
the emulsion initiator is one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate; preferably one or two of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate; a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate in a mass ratio of 3:2 is preferred.
The initiator a is one or more of azobisisobutyronitrile, azobisisobutyric acid and dimethyl azobisisobutyrate; preferably one or two of azodiisobutyronitrile and azodiisobutyronitrile; more preferably a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 3: 1.
The initiator b is one or more of azobisisovaleronitrile, azobisisoheptonitrile and azobiscyanovaleric acid; preferably one or two of azodicyano valeric acid and azodiisoheptonitrile; a composition of azobiscyanovaleric acid and azobisisoheptonitrile in a mass ratio of 1:1 is preferred.
Wherein the initiation rate of initiator b is higher than that of initiator a.
Specifically, the liquid film reinforcing agent is one or more of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose. Preferably one or two of polyvinylpyrrolidone and hydroxypropyl cellulose; more preferably a composition of polyvinylpyrrolidone and hydroxypropylcellulose in a mass ratio of 1: 1.
Specifically, the polyether is prepared from the following components in a mass ratio of 2:1 of copolyether of ethylene oxide and propylene oxide, the mass ratio of 3:2, copolyether of ethylene oxide and propylene oxide, with a mass ratio of 1:1 of one or more of copolyethers of ethylene oxide and propylene oxide. Preferably, the mass ratio is 2:1 copolyethers of ethylene oxide and propylene oxide.
Specifically, the cross-linking agent is one or two of pyromellitic dianhydride hydroxyethyl dimethacrylate and di (methacryloyloxyethyl) pyromellitic dianhydride ester. Preferably a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 2: 1.
Specifically, the chain transfer agent is sodium methallyl sulfonate.
Specifically, the neutralizer is one or more of 30% solubility sodium hydroxide solution, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate. Preferably one or more of potassium hydroxide, sodium carbonate and sodium bicarbonate; more preferably a combination of sodium carbonate and sodium bicarbonate in a mass ratio of 2: 5.
Specifically, the pH regulator is one or more of sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine. Preferably one or more of sodium ethoxide, diethanolamine and triisopropanolamine; more preferably a composition of diethanolamine and triisopropanolamine in a mass ratio of 1: 1.
Another object of the present invention is to provide a modified hydroxy ester based polymer waterproof coating prepared by the above method.
The raw materials for preparing the modified hydroxyl ester-based polymer comprise the following components in parts by mass in 1000 parts by mass:
1.0-4.2 parts of hydrophilic small monomer for emulsification;
1.7-4.5 parts of hydrophobic small monomer for emulsification;
18-51 parts of hydroxyl hydrophilic small monomer;
380-450 parts of ester hydrophobic small monomer;
0.05-0.26 part of emulsion initiator;
2.2-5.4 parts of an initiator a;
3.5-6.6 parts of an initiator b;
6.2-9.3 parts of a cross-linking agent;
0.06-0.28 part of chain transfer agent;
0.5-1.0 part of graphene oxide;
15-40 parts of polyether;
6.81-15.24 parts of super-concentrated emulsifier;
2.0-6.5 parts of auxiliary emulsifier;
0.4-1.3 parts of liquid film intensifier;
5-10 parts of a pH regulator;
5-10 parts of a neutralizing agent;
the balance of water.
The invention has the beneficial effects that:
the waterproof material adopts a hydroxyl and ester group small monomer matched with a super-concentrated emulsion polymerization method, and a hydroxyl ester group polymer waterproof coating is synthesized by using the super-concentrated emulsion polymerization method, 2 initiators are used in the polymerization reaction process, more reaction monomers are used in the front stage of the polymerization reaction in the front stage time of the polymerization reaction, the reaction rate is high, the initiators are easy to contact with the reaction monomers to initiate the polymerization reaction, so that the initiators with slightly weak activity can be used, and the cost is saved; in the later stage of the polymerization reaction, most monomers already form polymers, and the chance of the contact of the initiator and the reaction monomers is reduced, so that the initiator with stronger activity is used in the later stage of the reaction, the reaction is promoted, and the reaction is more complete. In addition, the following effects are provided:
1. according to the invention, the hydroxyl hydrophilic small monomer and the ester hydrophobic small monomer are compounded with the graphene oxide and the cross-linking agent, the plasticity of the polymer is increased by adding the graphene oxide, and the polymer has good flexibility at low temperature, is easy to coat and has excellent low-temperature flexibility. The addition of the cross-linking agent enhances the coupling force between the reaction monomers, the reaction is more complete, and the reaction effect is better.
2. The invention uses the super-concentrated emulsion polymerization method, does not use the traditional emulsifier when using the super-concentrated emulsion polymerization method, but uses the compound water of the hydrophilic small monomer and the hydrophobic small monomer and the super-concentrated initiator to prepare the super-concentrated emulsifier, and then prepares the compound emulsifier aqueous solution, so the prepared super-concentrated emulsion is also a soap-free emulsion at the same time, and the reaction efficiency is higher.
3. In the process of carrying out polymerization reaction, 2 kinds of initiators are used, more reaction monomers are used in the front stage of the polymerization reaction in the front stage time of the polymerization reaction, the reaction rate is high, and the initiators are easy to contact with the reaction monomers to initiate the polymerization reaction, so that the initiators with weak activity can be used, and the cost is saved; in the later stage of the polymerization reaction, most monomers already form polymers, and the chance of the contact of the initiator and the reaction monomers is reduced, so that the initiator with stronger activity is used in the later stage of the reaction, the reaction is promoted, and the reaction is more complete.
4. The hydrophilic small monomer adopted by the invention is a hydroxyl small monomer, and the hydroxyl has strong ability of complexing calcium ions, can be well adsorbed on the surface of a wall body, and has very excellent adsorbability.
5. The polyether is adopted, so that the defoaming capability of the emulsion is enhanced, the reaction is not interfered by bubbles, the reaction rate is increased, and the formed polymer coating is smoother and has more excellent waterproof effect.
6. The waterproof coating is suitable for being mixed with cement, a large number of hydroxyl groups can stably complex calcium ions, hydrolysis of the calcium ions is effectively inhibited, the strength of the cement is improved, the waterproof effect is enhanced, the internal bonding force of a polymer can be enhanced through the hydroxyl group intramolecular hydrogen bonds, the adhesive force between the polymer and a matrix is enhanced through the strong hydrophilic effect, and the waterproof coating is very suitable for being used as the waterproof coating for the cement.
7. According to the invention, the excellent mechanical property of graphene oxide is utilized, so that the tensile strength of the polymer emulsion formed film is obviously increased; the water resistance is also improved to a certain extent. In addition, the rich oxygen-containing functional groups of the graphene oxide can regulate the growth of cement hydration product crystals and improve the tensile strength and toughness of the cement hydration product; therefore, the graphene oxide modified polymer cement waterproof coating has good durability, impermeability and physical and mechanical properties, and has a wide application prospect.
Detailed Description
The invention will be further illustrated with reference to specific examples, to which the present invention is not at all restricted.
Example 1
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
1.3 parts of allyl alcohol;
4.5 parts of n-butyl (meth) acrylate;
42 parts of methyl allyl alcohol;
380 parts of 2-phenoxyethyl methacrylate;
0.09 part of lauroyl peroxide;
2.9 parts of azobisisobutyronitrile;
6.1 parts of azobisisovaleronitrile;
6.2 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;
0.15 part of sodium methallyl sulfonate;
0.7 part of graphene oxide;
the mass ratio is 2: 39 parts of a copolyether of ethylene oxide and propylene oxide of 1;
10.74 parts of super concentrated emulsifier;
5.0 parts of hexadecane;
1.0 part of polyvinyl alcohol;
6.8 parts of sodium methoxide;
7.3 parts of 30 percent sodium hydroxide solution;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) 4.7 parts of water, 1.3 parts of allyl alcohol, 4.5 parts of n-butyl (meth) acrylate, 0.09 part of lauroyl peroxide and 0.15 part of sodium methallylsulfonate are directly added into a three-neck flask with a stirring device, and after uniform stirring, the reaction is carried out for 1.5 hours at the temperature of 70 ℃, and then the reaction is carried out for 1.5 hours under heat preservation, and the super-concentrated emulsifier is obtained after cooling.
2) 42 parts of methyl allyl alcohol, 380 parts of 2-phenoxyethyl methacrylate, 6.2 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate and 39 parts of 2:1, adding copolyether of ethylene oxide and propylene oxide and 0.7 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 6.8 parts of sodium methoxide to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 12 parts of deionized water, 10.74 parts of prepared super-concentrated emulsifier, 5.0 parts of hexadecane and 1.0 part of polyvinyl alcohol into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump, dropwise adding for 1.5 hours, and continuously stirring for 15 minutes after dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 3 minutes at the speed of 1150 revolutions per minute;
6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 70 ℃ water bath, keeping the temperature constant for 8 hours, firstly dripping the solution A for 6 hours, and then dripping the solution B for 2 hours, wherein the solution A comprises 50 parts of water and 2.9 parts of azobisisobutyronitrile, and the solution B comprises 50 parts of water and 6.1 parts of azobisisovaleronitrile;
7) after the reaction is finished, preserving heat, curing for 2 hours, cooling, adding 7.3 parts of 30% solubility sodium hydroxide solution, and supplementing water until the mass of the total solution is 1000 parts, thereby preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Example 2
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
1.3 parts of methyl allyl alcohol;
4.5 parts of isobutyl (meth) acrylate;
42 parts of isopentenol;
380 parts of 2-propylheptyl acrylate;
0.09 part of tert-butyl peroxypivalate;
2.9 parts of azodiisobutyric acid;
6.1 parts of azodicyano valeric acid;
6.2 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester;
0.15 part of sodium methallyl sulfonate;
0.7 part of graphene oxide;
the mass ratio is 3: 39 parts of a copolyether of ethylene oxide and propylene oxide of 2;
10.74 parts of super concentrated emulsifier;
5.0 parts of hexadecanol;
1.0 part of polyvinylpyrrolidone;
6.8 parts of sodium ethoxide;
7.3 parts of potassium hydroxide;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) 4.7 parts of water, 1.3 parts of methyl allyl alcohol, 4.5 parts of isobutyl (methyl) acrylate, 0.09 part of tert-butyl peroxypivalate and 0.15 part of sodium methallylsulfonate are directly added into a three-neck flask with a stirring device, after uniform stirring, the temperature is controlled to react for 1.5 hours at 70 ℃, then the temperature is kept for 1.5 hours, and the ultra-concentrated emulsifier is obtained after cooling.
2) 42 parts of isopentenol, 380 parts of 2-propylheptyl acrylate, 6.2 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester, and 39 parts of a mixture of 3:2, adding the copolyether of ethylene oxide and propylene oxide and 0.7 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 6.8 parts of sodium ethoxide to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 12 parts of deionized water, 10.74 parts of the prepared super-concentrated emulsifier, 5.0 parts of hexadecanol and 1.0 part of polyvinylpyrrolidone into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump, dropwise adding for 1.5 hours, and continuously stirring for 15 minutes after dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 3 minutes at the speed of 1150 revolutions per minute;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 70 ℃ water bath for constant temperature of 8 hours, firstly dripping the solution A for 6 hours, and then dripping the solution B for 2 hours, wherein the solution A comprises 50 parts of water and 2.9 parts of azobisisobutyric acid, and the solution B comprises 50 parts of water and 6.1 parts of azobiscyanovaleric acid;
7) after the reaction is finished, preserving heat, curing for 2 hours, cooling, adding 7.3 parts of potassium hydroxide, and supplementing water until the mass of the total solution is 1000 parts, thereby preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Example 3
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
3.7 parts of isopentenol;
2.4 parts of lauryl (meth) acrylate;
26 parts of 4- (ethyleneoxy) -1-butanol;
410 parts of methacryloyloxyethyl phthalic monoester;
0.17 part of dicyclohexyl peroxydicarbonate;
3.4 parts of dimethyl azodiisobutyrate;
3.7 parts of azobisisoheptonitrile;
8.5 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;
0.08 part of sodium methallyl sulfonate;
0.5 part of graphene oxide;
the mass ratio is 1: 26 parts of copolyether of ethylene oxide and propylene oxide of 1;
12.25 parts of super concentrated emulsifier;
6.5 parts of octadecyl methacrylate;
1.3 parts of hydroxypropyl cellulose;
5.7 parts of ethanolamine;
8.4 parts of sodium carbonate;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) directly adding 5.9 parts of water, 3.7 parts of isopentenol, 2.4 parts of (methyl) lauryl acrylate, 0.17 part of dicyclohexyl peroxydicarbonate and 0.08 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1 hour at 85 ℃, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.
2) 26 parts of 4- (ethyleneoxy) -1-butanol, 410 parts of methacryloyloxyethyl phthalate monoester, 8.5 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate and 26 parts of 1:1, adding copolyether of ethylene oxide and propylene oxide and 0.5 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.7 parts of ethanolamine to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 5-16 parts of deionized water, 12.25 parts of prepared super-concentrated emulsifier, 6.5 parts of octadecyl methacrylate and 1.3 parts of hydroxypropyl cellulose into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump for 2 hours, and continuously stirring for 12 minutes after the dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 4 minutes at the speed of 1000 revolutions per minute;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 70 ℃ water bath, keeping the temperature constant for 8 hours, firstly dripping the solution A for 7 hours, and then dripping the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 3.4 parts of dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 3.7 parts of azodiisoheptonitrile;
7) after the reaction is finished, preserving heat, curing for 1.5 hours, cooling, adding 8.4 parts of sodium carbonate, and supplementing water until the mass of the total solution is 1000 parts, thereby preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Example 4
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
3.7 parts of a composition of the propylene alcohol and the isopentenol in a mass ratio of 1: 1;
2.4 parts of a composition of lauryl (meth) acrylate and 2-ethylhexyl (meth) acrylate in a mass ratio of 1: 3;
26 parts of a composition of methacrylic alcohol and isopentenol in a mass ratio of 1: 2;
410 parts of a composition of 2:1 mass ratio of methacryloyloxyethyl phthalate monoester to 2-methacryloyloxyethyl ester;
0.17 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate in a mass ratio of 3: 2;
3.4 parts of a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 3: 1;
3.7 parts of a composition of azobiscyanovaleric acid and azobisisoheptonitrile in a mass ratio of 1: 1;
8.5 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 2: 1;
0.08 part of sodium methallyl sulfonate;
0.5 part of graphene oxide;
the mass ratio is 2: 26 parts of copolyether of ethylene oxide and propylene oxide of 1;
12.25 parts of super concentrated emulsifier;
6.5 parts of a composition of stearyl methacrylate and hexadecane in a mass ratio of 3: 4;
1.3 parts of a composition of polyvinylpyrrolidone and hydroxypropyl cellulose in a mass ratio of 1: 1;
5.7 parts of a composition of diethanolamine and triisopropanolamine in a mass ratio of 1: 1;
8.4 parts of a composition of sodium carbonate and sodium bicarbonate with the mass ratio of 2: 5;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) 5.9 parts of water, 3.7 parts of a composition of propylene alcohol and isopentenol in a mass ratio of 1:1, 2.4 parts of a composition of lauryl (meth) acrylate and 2-ethylhexyl (meth) acrylate in a mass ratio of 1:3, 0.17 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate in a mass ratio of 3:2 and 0.08 part of sodium methallylsulfonate are directly added into a three-neck flask with a stirring device, the mixture is uniformly stirred, the temperature is controlled to be 85 ℃ for reaction for 1 hour, the mixture is kept warm for 1 hour, and the super-concentrated emulsifier is obtained after cooling.
2) 26 parts of a composition of methacrylic alcohol and isopentenol in a mass ratio of 1:2, 410 parts of a composition of methacryloxyethyl phthalate monoester and 2-methacryloxyethyl ester in a mass ratio of 2:1, 8.5 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloxyethyl) pyromellitic dianhydride ester in a mass ratio of 2:1, 26 parts of a composition of 2: adding 1 part of copolyether of ethylene oxide and propylene oxide and 0.5 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.7 parts of a composition of diethanolamine and triisopropanolamine in a mass ratio of 1:1, adjusting the pH to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 5-16 parts of deionized water, 12.25 parts of the prepared super-concentrated emulsifier, 6.5 parts of a composition of octadecyl methacrylate and hexadecane in a mass ratio of 3:4 and 1.3 parts of a composition of polyvinylpyrrolidone and hydroxypropyl cellulose in a mass ratio of 1:1 into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump for 2 hours, and continuously stirring for 12 minutes after the dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 4 minutes at the speed of 1000 revolutions per minute;
6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 70 ℃ water bath for constant temperature 8 hours, firstly dripping the solution A for 7 hours, and then dripping the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 3.4 parts of a composition of azodiisobutyronitrile and azodiisobutyronitrile in a mass ratio of 3:1, and the solution B comprises 50 parts of water and 3.7 parts of a composition of azodicyano valeric acid and azodiisoheptonitrile in a mass ratio of 1: 1;
7) after the reaction is finished, preserving heat, curing for 1.5 hours, cooling, adding 8.4 parts of a composition of sodium carbonate and sodium bicarbonate with the mass ratio of 2:5, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Example 5
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
4.2 parts of allyl alcohol;
4.5 parts of 2-ethylhexyl (meth) acrylate;
19 parts of 4- (ethyleneoxy) -1-butanol;
400 parts of 2-methacryloyloxyethyl ester;
0.21 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate in a mass ratio of 3: 2;
5.2 parts of a composition of azobisisobutyronitrile and dimethyl azobisisobutyrate in a mass ratio of 1: 1;
5.4 parts of azodicyano valeric acid;
7.7 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 1: 1;
0.28 part of sodium methallyl sulfonate;
1.0 part of graphene oxide;
the mass ratio is 3: 40 parts of copolyether of ethylene oxide and propylene oxide of 2;
14.49 parts of super concentrated emulsifier;
2.5 parts of octadecyl acrylate;
0.5 part of polyvinyl alcohol;
9.2 parts of diethanolamine;
6.6 parts of sodium bicarbonate;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) directly adding 5.3 parts of water, 4.2 parts of allyl alcohol, 4.5 parts of 2-ethylhexyl (meth) acrylate, 0.21 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate in a mass ratio of 3:2 and 0.28 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 82 ℃ for 1.5 hours, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.
2) 19 parts of 4- (ethyleneoxy) -1-butanol, 400 parts of 2-methacryloyloxyethyl ester, 7.7 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and di (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 1:1, 40 parts of a mixture of 3:2, adding 1.0 part of graphene oxide and copolyether of ethylene oxide and propylene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 9.2 parts of diethanolamine to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 7 parts of deionized water, 14.49 parts of prepared super-concentrated emulsifier, 2.5 parts of octadecyl acrylate and 0.5 part of polyvinyl alcohol into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump for 2 hours, and continuously stirring for 19 minutes after the dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 3 minutes at the speed of 900 revolutions per minute;
6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a water bath at 80 ℃ for 6 hours at constant temperature, firstly dripping the solution A for 5 hours, and then dripping the solution B for 1 hour, wherein the solution A consists of 50 parts of water and 5.2 parts of a composition of azobisisobutyronitrile and dimethyl azobisisobutyrate in a mass ratio of 1:1, and the solution B consists of 50 parts of water and 5.4 parts of azobiscyanovaleric acid;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 6.6 parts of sodium bicarbonate, and supplementing water until the mass of the total solution is 1000 parts, thereby preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Example 6
The raw materials for preparing the hydroxyl ester-based polymer waterproof coating comprise the following components:
4.2 parts of methyl allyl alcohol;
4.5 parts of octadecyl (meth) acrylate;
19 parts of allyl alcohol;
400 parts of methacryloyloxyethyl hexahydrophthalic monoester;
0.21 part of lauroyl peroxide;
5.2 parts of dimethyl azodiisobutyrate;
5.4 parts of azodicyano valeric acid;
7.7 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 1: 1;
0.28 part of sodium methallyl sulfonate;
1.0 part of graphene oxide;
the mass ratio is 3: 40 parts of copolyether of ethylene oxide and propylene oxide of 2;
14.49 parts of super concentrated emulsifier;
2.5 parts of lauryl methacrylate;
0.5 part of polyvinylpyrrolidone;
9.2 parts of triethanolamine;
6.6 parts of potassium carbonate;
the balance of water.
The total mass is 1000 percent, and the solid content is 50 percent
The preparation method of the hydroxyl ester-based polymer waterproof coating is formed by polymerizing the following components in parts by weight, and comprises the following specific steps:
1) directly adding 5.3 parts of water, 4.2 parts of methyl allyl alcohol, 4.5 parts of octadecyl (meth) acrylate, 0.21 part of lauroyl peroxide and 0.28 part of sodium methallylsulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 82 ℃ for 1.5 hours, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.
2) 19 parts of allyl alcohol, 400 parts of methacryloxyethyl hexahydrophthalic monoester, 7.7 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and di (methacryloxyethyl) pyromellitic dianhydride in a mass ratio of 1:1, 40 parts of a mixture of 3:2, adding 1.0 part of graphene oxide and copolyether of ethylene oxide and propylene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 9.2 parts of triethanolamine, adjusting the pH value to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 7 parts of deionized water, 14.49 parts of prepared super-concentrated emulsifier, 2.5 parts of lauryl methacrylate and 0.5 part of polyvinylpyrrolidone into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump for 2 hours, and continuously stirring for 19 minutes after the dropwise adding is finished to prepare the super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 3 minutes at the speed of 900 revolutions per minute;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a water bath at 80 ℃ for 6 hours at constant temperature, firstly dropwise adding the solution A for 5 hours, and then dropwise adding the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 5.2 parts of dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 5.4 parts of azodicyano valeric acid;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 6.6 parts of potassium carbonate, and supplementing water until the mass of the total solution is 1000 parts, thereby preparing the hydroxyl ester-based polymer with the mass fraction of 50%.
Performance test Table for products of examples
Figure BDA0002214848190000141
Figure BDA0002214848190000151
As can be seen from the above table, the hydroxyl ester based super-concentrated emulsion polymer waterproof coating of the present invention has excellent performance required by the market, and the performance thereof is superior to that of the traditional waterproof coating. The combination of example 4 shows that the invention has the advantages of excellent performance, stable property, long service life, good ductility, high tensile strength, wear resistance, impact resistance, no after tack, quick surface drying time and short secondary construction time. And because of the strong complexing ability with cement, the preparation method is very applicable to cement, and the preparation method is simple and convenient, has low requirements on production process and equipment, and is suitable for mass production and large-area construction.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of modified hydroxyl ester-based polymer emulsion is characterized by comprising the following steps:
1) directly adding 4.0-6.0 parts of water, 1.0-4.2 parts of hydrophilic small monomer for emulsification, 1.7-4.5 parts of hydrophobic small monomer for emulsification, 0.05-0.26 part of emulsion initiator and 0.06-0.28 part of chain transfer agent into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 70-90 ℃ for 1-2 hours, preserving heat for 1-2 hours, and cooling to obtain the super-concentrated emulsifier;
the hydrophilic small monomer for emulsification is one or more of allyl alcohol, methyl allyl alcohol and isoamylol alcohol;
the hydrophobic small monomers for emulsification are ester-based hydrophobic monomers and are one or more of n-butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) acrylate and benzyl methacrylate;
2) adding 18-51 parts of hydroxyl hydrophilic small monomer, 380-450 parts of ester hydrophobic small monomer, 6.2-9.3 parts of cross-linking agent, 15-40 parts of polyether and 0.5-1.0 part of graphene oxide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5-10 parts of pH regulator to adjust the pH value to 8-8.5, and uniformly stirring to obtain a reaction mixed monomer;
the hydroxyl hydrophilic small monomer is one or more of allyl alcohol, methyl allyl alcohol, isopentenol and 4- (ethyleneoxy) -1-butanol;
the ester hydrophobic small monomer is one or more of 2-phenoxyethyl methacrylate, 2-propylheptyl acrylate, methacryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl ester and methacryloyloxyethyl hexahydrophthalate monoester;
3) adding 5-16 parts of deionized water, 6.81-15.24 parts of prepared super-concentrated emulsifier, 2.0-6.5 parts of co-emulsifier and 0.4-1.3 parts of liquid film reinforcing agent into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 1-3 hours to prepare a composite emulsifier aqueous solution;
4) dropwise adding the reaction monomer mixed solution into the composite emulsifier aqueous solution under the stirring condition through a dropwise adding pump, dropwise adding for 1.5-2 hours, and continuously stirring for 10-20 minutes after dropwise adding is finished to prepare super-concentrated emulsion;
5) transferring the super-concentrated emulsion into a centrifugal test tube at room temperature, and centrifuging for 2-4 minutes at the speed of 900-;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a water bath at 65-80 ℃ for 6-8 hours at constant temperature, firstly dripping the solution A for 5-7 hours, and then dripping the solution B for 1-2 hours, wherein the solution A comprises 50 parts of water and 2.2-5.4 parts of initiator a, and the solution B comprises 50 parts of water and 3.5-6.6 parts of initiator B;
7) after the reaction is finished, preserving heat, curing for 1-2 hours, cooling, adding 5-10 parts of neutralizing agent, and supplementing water until the total solution mass is 1000 parts.
2. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the auxiliary emulsifier is one or more of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate.
3. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the emulsion initiator is one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate; the initiator a is one or more of azobisisobutyronitrile, azobisisobutyric acid and dimethyl azobisisobutyrate; the initiator b is one or more of azobisisovaleronitrile, azobisisoheptonitrile and azobiscyanovaleric acid; wherein the initiation rate of initiator b is higher than that of initiator a.
4. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the liquid film reinforcing agent is one or more of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose.
5. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the polyether is prepared from the following components in percentage by mass: 1 of copolyether of ethylene oxide and propylene oxide, the mass ratio of 3:2, copolyether of ethylene oxide and propylene oxide, with a mass ratio of 1:1 of one or more of copolyethers of ethylene oxide and propylene oxide.
6. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the cross-linking agent is one or two of pyromellitic dianhydride hydroxyethyl dimethacrylate and di (methacryloyloxyethyl) pyromellitic dianhydride ester.
7. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the chain transfer agent is sodium methallyl sulfonate.
8. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the neutralizer is one or more of 30% solubility sodium hydroxide solution, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate.
9. The method of claim 1, wherein the modified hydroxy ester based polymer emulsion comprises: the pH regulator is one or more of sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.
10. A modified hydroxy ester based polymer emulsion characterized by: prepared by the method of any one of claims 1 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995718A (en) * 2020-09-04 2020-11-27 武汉纺织大学 Nonionic and acidic side group modified polyacrylic acid thickener and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6262163B1 (en) * 1998-05-14 2001-07-17 Wacker Chemie Gmbh Process for preparing protective-colloid-stabilized vinyl ester or vinyl ester-ethylene polymers in the form of their aqueous dispersions
CN1438253A (en) * 2003-03-06 2003-08-27 华南理工大学 Acrylate micro-emulsion with high solid content, its preparation method and use
WO2008133375A1 (en) * 2007-04-27 2008-11-06 Youngwoo Chemtech Co., Ltd. Acrylic acid ester copolymer composition and redispersible powders
US20100247786A1 (en) * 2007-11-21 2010-09-30 Base Se New polymers by emulsion polymerization
CN102827322A (en) * 2012-08-14 2012-12-19 华南理工大学 Preparation method and application of internal-external dual cross-linked core-shell structured acrylic acid emulsion
CN105601835A (en) * 2015-11-18 2016-05-25 吉林建筑大学 Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof
CN106318091A (en) * 2016-08-19 2017-01-11 北京金汇利应用化工制品有限公司 Resin for novel waterborne double-component organic-inorganic hybrid coating and preparation method of resin
CN108689648A (en) * 2018-08-21 2018-10-23 合肥易多方科技有限公司 Acrylate copolymer cement waterproof paint
CN109422835A (en) * 2017-06-30 2019-03-05 翁秋梅 A kind of dynamic aggregation object containing combination supermolecular mechanism

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6262163B1 (en) * 1998-05-14 2001-07-17 Wacker Chemie Gmbh Process for preparing protective-colloid-stabilized vinyl ester or vinyl ester-ethylene polymers in the form of their aqueous dispersions
CN1438253A (en) * 2003-03-06 2003-08-27 华南理工大学 Acrylate micro-emulsion with high solid content, its preparation method and use
WO2008133375A1 (en) * 2007-04-27 2008-11-06 Youngwoo Chemtech Co., Ltd. Acrylic acid ester copolymer composition and redispersible powders
US20100247786A1 (en) * 2007-11-21 2010-09-30 Base Se New polymers by emulsion polymerization
CN102827322A (en) * 2012-08-14 2012-12-19 华南理工大学 Preparation method and application of internal-external dual cross-linked core-shell structured acrylic acid emulsion
CN105601835A (en) * 2015-11-18 2016-05-25 吉林建筑大学 Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof
CN106318091A (en) * 2016-08-19 2017-01-11 北京金汇利应用化工制品有限公司 Resin for novel waterborne double-component organic-inorganic hybrid coating and preparation method of resin
CN109422835A (en) * 2017-06-30 2019-03-05 翁秋梅 A kind of dynamic aggregation object containing combination supermolecular mechanism
CN108689648A (en) * 2018-08-21 2018-10-23 合肥易多方科技有限公司 Acrylate copolymer cement waterproof paint

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995718A (en) * 2020-09-04 2020-11-27 武汉纺织大学 Nonionic and acidic side group modified polyacrylic acid thickener and preparation method thereof
CN111995718B (en) * 2020-09-04 2022-03-18 武汉纺织大学 Nonionic and acidic side group modified polyacrylic acid thickener and preparation method thereof

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