CN110698587A - Preparation method of high-performance super-concentrated emulsion polymer - Google Patents
Preparation method of high-performance super-concentrated emulsion polymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-performance super-concentrated emulsion polymer. The required raw materials are as follows: 2.3-5.5 parts of hydrophilic small monomer for emulsification, 5.4-9.2 parts of hydrophobic small monomer for emulsification, 5-19 parts of sulfonic small monomer, 0.10-0.45 part of emulsion initiator, 2.5-5.3 parts of initiator a, 4.1-6.6 parts of initiator b, 0.21-0.62 part of chain transfer agent, 390-445 parts of ester-based small monomer, 4.7-8.9 parts of cross-linking agent, 3.9-8.5 parts of rigid small monomer, 19-40 parts of polyether, 0.1-0.9 part of graphene oxide, 9.7-20.6 parts of neutralizing agent, 5.5-9.7 parts of pH regulator, 1.0-4.5 parts of auxiliary emulsifying agent, 0.2-0.9 part of reinforcing agent, and the balance of water, wherein the total mass part is 1000 and the solid content is 50%. The invention adopts a super-concentrated emulsion polymerization method by using sulfonic small monomers and ester small monomers, and the invention adds the co-emulsifier and the liquid film intensifier to promote the emulsification effect in the preparation process, so that the super-concentrated emulsion is more stable. The polyether is adopted in the preparation process, and plays a defoaming role in the reaction process, so that reactants are contacted more fully, the reaction is promoted, and the coating is more convenient to paint.
Description
Technical Field
The invention belongs to the technical field of building waterproof materials, and particularly relates to a preparation method of a high-performance super-concentrated emulsion polymer.
Background
Along with the increasing progress of science and technology and the increasing improvement of living conditions of people, the nation also puts forward stricter requirements on the building material industry, and the strength, the waterproof performance, the high temperature resistance and the freezing resistance of the building material are required to be obviously improved. Namely, the building material is required to have high strength, high water resistance, high durability and the like. Thus, high-performance waterproof coatings have been rapidly developed. The excellent waterproof material is widely applied to various waterproof projects, can be used in various building processes in a humid environment by virtue of excellent waterproofness, and has more excellent performance and wider application occasions compared with the traditional waterproof coating.
As building materials are increasingly required, the development of waterproof coatings is inevitable. The novel waterproof material is prepared from the hydrophilic monomer and the hydrophobic monomer in a super-concentrated emulsion system, and the waterproof coating has excellent waterproof performance which is not possessed by the conventional waterproof material, and the tensile elasticity, the bonding force, the durability and the high temperature resistance of the waterproof coating are greatly improved, so that the waterproof coating is excellent in performance.
Patent CN107987576A discloses a waterproof paint, which comprises the following components in parts by weight: 30-60 parts of ethyl acrylate, 15-30 parts of a flame retardant, 30-60 parts of water, 0-10 parts of talcum powder, 0-10 parts of high-alumina bauxite, 0-10 parts of titanium dioxide, 1-3 parts of a dispersing agent, 0.5-1 part of a film-forming assistant, 0.5-1 part of a defoaming agent and 3-5 parts of ammonium persulfate. The flame-retardant waterproof coating for the magnesium alloy battery box of the new energy automobile, which is prepared by the invention, has excellent waterproof and flame-retardant properties, is low in manufacturing cost, convenient to use, strong in corrosion resistance and weather resistance, environment-friendly and excellent in storage resistance, and can meet various requirements of the magnesium alloy battery box of the new energy automobile on flame-retardant and waterproof coating.
The invention discloses a preparation method of a waterproof coating, which relates to a preparation method of a flame-retardant waterproof coating, and the preparation method comprises the steps of dissolving 3-7g of hexadecyl trimethyl ammonium bromide in 150ml of distilled water, stirring and dissolving, adding 5-15g of calcium-based montmorillonite, stirring for 6-18h at room temperature, carrying out suction filtration to obtain a filter cake, repeatedly washing the filter cake with distilled water until no precipitate is detected by using 0.1mol/L AgNO3 solution, drying, grinding and sieving with a 200-mesh sieve to obtain modified montmorillonite; diluting 6g of each fluorosilicone resin with water to 30g, adding 0.2-0.4g of surfactant triton and 2-5g of modified montmorillonite, and stirring at room temperature for 1-2 h; then adding 0.7-1.2g of ammonium polyphosphate, 0.1-0.5g of melamine and 0.1-0.3g of zinc borate, stirring for 1-3h at 40-60 ℃, adding 0.3-0.5g of drier, and continuously stirring for 20-30min to obtain the product; the invention has the advantages of environmental protection, good flame-retardant and waterproof effects, low cost, good toughness of the coating film and strong practical application value.
The patent CN102911418A discloses a method for preparing a polyacrylate-organic P flame retardant by using super-concentrated emulsion, which is characterized in that tributyl phosphate, styrene, acrylonitrile and butyl methacrylate monomers are mainly used for synthesizing a polyacrylate prepolymer, then the polyacrylate prepolymer is dropwise added into a water phase consisting of polyvinyl alcohol, deionized water and sodium dodecyl sulfate at room temperature to obtain jelly-like emulsion, the jelly-like emulsion is transferred into a centrifuge tube, and the jelly-like emulsion is centrifuged for about 1-3 minutes to remove bubbles on the upper layer; then introducing nitrogen, sealing by a rubber plug, and placing in a water area at 50 ℃ for polymerization reaction for 24 hours to prepare the tributyl phosphate polymer flame retardant with different mass fractions.
When the waterproof coating in the prior art is subjected to ultra-concentrated emulsification, the traditional emulsifier is used, the emulsification effect and efficiency are poor, the prepared coating is poor in adhesion, heat resistance and tensile resistance, the performance and service life of the coating are affected, and the comprehensive performance of the coating has a larger promotion space.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-performance super-concentrated emulsion polymer.
The polymer waterproof coating with good waterproof effect is prepared by adopting the hydrophobic small monomer and the hydrophilic small monomer by using a super-concentrated emulsion polymerization method, and has the properties of good connection property, good tensile strength, high temperature resistance and the like.
The method adopts a super-concentrated emulsion polymerization method, the high concentration of the super-concentrated emulsion reduces the mobility of monomers in vacuole, and delays the termination of molecular chains, thereby accelerating the reaction rate and increasing the molecular weight. And the size of the vacuole can be controlled by changing the pH value or the ionic strength, so that the size of the polymer latex particles can be better adjusted.
The technical scheme provided by the invention is as follows:
a preparation method of a high-performance super concentrated emulsion polymer comprises the following steps:
1) directly adding 2.5-6.0 parts of water, 2.3-5.5 parts of hydrophilic small monomer for emulsification, 5.4-9.2 parts of hydrophobic small monomer for emulsification, 0.10-0.45 part of emulsion initiator and 0.21-0.62 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 a super-concentrated emulsifier;
the hydrophilic small monomer for emulsification is a sulfonic hydrophilic monomer, and is one or two of sodium vinyl sulfonate and sodium propenyl sulfonate; preferably a composition of sodium vinyl sulfonate and sodium propenyl sulfonate in a mass ratio of 3: 2;
the hydrophobic small monomer for emulsification is an ester group hydrophobic monomer and is one or more of n-butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) acrylate and benzyl methacrylate; preferably one or more of n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octadecyl (meth) acrylate, and benzyl methacrylate; more preferably a composition of 2-ethylhexyl (meth) acrylate and benzyl methacrylate in a mass ratio of 1: 3;
the chain transfer agent is sodium hypophosphite;
2) adding 5-19 parts of sulfonic hydrophilic small monomer, 390-445 parts of ester hydrophobic small monomer, 4.7-8.9 parts of cross-linking agent, 19-40 parts of polyether, 0.1-0.9 part of graphene oxide and 3.9-8.5 parts of rigid small monomer into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.5-9.7 parts of pH regulator to adjust the pH value to 8-8.5, and uniformly stirring;
the sulfonic hydrophilic monomer is one or more of sodium methallyl sulfonate, sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid; preferably one or two of sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid; more preferably a combination of sodium styrene sulfonate and 2-acrylamido-2-methylpropanesulfonic acid in a mass ratio of 2: 1;
one or more of ester group hydrophobic monomer 2-phenoxyethyl methacrylate, 2-propylheptyl acrylate, methacryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl ester and methacryloyloxyethyl hexahydrophthalate monoester; preferably one or more of 2-propylheptyl acrylate, methacryloyloxyethyl phthalate monoester and 2-methacryloyloxyethyl ester; more preferably a composition of 2-propylheptyl acrylate and 2-methacryloyloxyethyl ester in a mass ratio of 1: 1;
3) adding 8-20 parts of deionized water, 10.51-21.77 parts of prepared super-concentrated emulsifier, 1.0-4.5 parts of co-emulsifier and 0.2-0.9 part 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 65-85 ℃ for 6-8 hours at constant temperature, firstly dripping the solution A for 5-6 hours, and then dripping the solution B for 1-2 hours, wherein the solution A comprises 50 parts of water and 2.5-5.3 parts of initiator a, and the solution B comprises 50 parts of water and 4.1-6.6 parts of initiator B;
7) after the reaction is finished, preserving heat, curing for 1-2 hours, cooling, adding 9.7-20.6 parts of neutralizing agent, and supplementing water until the mass part of the total solution is 1000 to obtain the product.
Specifically, the coemulsifier is one or more of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate. Preferably one or more of cetyl alcohol, stearyl methacrylate and lauryl methacrylate; more preferably a composition of cetyl alcohol and lauryl methacrylate in a mass ratio of 1: 4.
Specifically, the liquid film reinforcing agent is one or more of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose. Preferably one or two of polyvinyl alcohol and polyvinylpyrrolidone; more preferably a composition of polyvinyl alcohol and polyvinylpyrrolidone in a mass ratio of 1: 1.
Specifically, the emulsion initiator is one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate. Preferably one or two of lauroyl peroxide and dicyclohexyl peroxydicarbonate; more preferably a combination of lauroyl peroxide and dicyclohexyl peroxydicarbonate in a mass ratio of 1: 1.
In particular, the method comprises the following steps of,
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 2: 3.
The initiator b is one or more of azobisisovaleronitrile, azobisisoheptonitrile and azobiscyanovaleric acid; preferably one or two of azodicyano valeric acid and azodiisoheptonitrile; more preferably a 1:1 mass ratio of azobiscyanovaleric acid and azobisisoheptonitrile.
Wherein the initiation rate of initiator b is higher than that of initiator a.
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 3: 2.
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 rigid small monomer is one or more of N-methylmaleimide, N-ethylmaleimide, 1-vinyl-2, 5-pyrrolidinedione, 1, 4-divinyl-2-azepane, 3-methyl-1-vinyl-2-azepane, (4-methylphenyl) azomethine, 1-phenylvinylboronic acid, 4-methoxy-2-vinylaniline, 2-aminostyrene, (4-methylphenyl) azomethine, N- (4-vinylbenzyl) -N, N-dimethylamine, 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene. Preferably one or more of N-ethylmaleimide, 1, 4-divinyl-2-azepane, 2-aminostyrene and (4-methylphenyl) azomethine; more preferably a composition of 1, 4-divinyl-2-azepane and 2-aminostyrene in a mass ratio of 2: 1.
In particular, the method comprises the following steps of,
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 sodium carbonate, sodium bicarbonate and potassium carbonate; more preferably a combination of sodium carbonate and potassium carbonate in a mass ratio of 4: 1.
The pH regulator is one or more of sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine; preferably one or more of sodium ethoxide, ethanolamine and triisopropanolamine; more preferably a combination of sodium ethoxide and triisopropanolamine in a mass ratio of 1: 2.
It is another object of the present invention to provide a high performance ultra-concentrated emulsion polymer prepared using the above process.
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass in total 1000 parts by mass:
2.3-5.5 parts of hydrophilic small monomer for emulsification;
5.4-9.2 parts of hydrophobic small monomer for emulsification;
5-19 parts of sulfonic hydrophilic small monomer;
390-445 parts of ester hydrophobic small monomer;
0.10-0.45 part of emulsion initiator;
2.5-5.3 parts of an initiator a;
4.1-6.6 parts of an initiator b;
4.7-8.9 parts of a cross-linking agent;
3.9-8.5 parts of rigid small monomer;
0.21-0.62 part of chain transfer agent;
19-40 parts of polyether;
0.1-0.9 part of graphene oxide;
10.51-21.77 parts of super-concentrated emulsifier;
1.0-4.5 parts of auxiliary emulsifier;
0.2-0.9 part of liquid film intensifier;
5.5-9.7 parts of a pH regulator;
9.7-20.6 parts of a neutralizing agent;
the balance of water.
The invention has the following beneficial effects:
the invention prepares a high molecular material containing sulfonic ester group, which adopts ester group hydrophobic small monomer to provide good hydrophobic effect for polymer, and compounds sulfonic hydrophilic small monomer on the basis of good hydrophobic property to increase the cohesiveness of polymer and building material, so that the polymer is not easy to fall off, the service life is greatly prolonged, and good heat resistance and tensile resistance are provided for polymer. In addition, the invention uses a super-concentrated emulsion polymerization method, and 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 that the prepared super-concentrated emulsion is also a soap-free emulsion at the same time, and the reaction efficiency is higher. Besides, the invention also has the following effects:
1. the invention prepares a high molecular material containing sulfonic ester group, which adopts ester group hydrophobic small monomer to provide good hydrophobic effect for polymer, and compounds sulfonic hydrophilic small monomer on the basis of good hydrophobic property to increase the cohesiveness of polymer and building material, so that the polymer is not easy to fall off, the service life is greatly prolonged, and good heat resistance and tensile resistance are provided for polymer.
2. The invention uses super-concentrated emulsion polymerization, the high concentration of super-concentrated emulsion reduces the mobility of monomer in vacuole, and delays the molecular chain termination, thereby quickening the reaction rate and increasing the molecular weight. And the size of the vacuole can be controlled by changing the pH value or the ionic strength, so that the size of the polymer latex particles can be better adjusted.
3. The pH value is adjusted to 8-8.5 in the reaction, the method is suitable for the polymerization of ester group hydrophobic monomers, the reaction polymerization is more sufficient, the molecular weight of the obtained polymer is larger under the pH value, the waterproof effect is greatly enhanced, and the added cross-linking agent ensures that the polymer molecules are more closely connected, the product is more stable and is not easy to decompose.
4. The invention uses two initiators with different initiating activities, more reaction monomers are used in the front stage time of the polymerization reaction, the reaction rate is higher, the initiators are easy to contact with the reaction monomers to initiate the polymerization reaction, so that the initiators with weaker 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.
5. The invention combines the advantages of a super-concentrated emulsion polymerization method and a soap-free emulsion polymerization method, prepares the super-concentrated emulsifier with the emulsifier effect, does not need the traditional emulsifier any more, can participate in the reaction of the super-concentrated emulsifier, does not need to remove the emulsifier subsequently, and saves the cost.
6. The polyether is adopted in the preparation process, and plays a defoaming role in the reaction process, so that reactants are contacted more fully, the reaction is promoted, and the coating is more convenient to paint.
7. In the preparation process, the auxiliary emulsifier and the liquid film enhancer are added to promote the emulsification effect, so that the ultra-concentrated emulsion is more stable.
8. According to the invention, the graphene oxide is added in the preparation process, so that the strength of a polymer system is improved, cracking is avoided, the tensile strength and toughness of a cement hydration product are improved, and the mechanical strength, durability and impermeability of the waterproof coating are improved.
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 high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
2.8 parts of sodium vinylsulfonate;
8.7 parts of 2-ethylhexyl (meth) acrylate;
12 parts of sodium styrene sulfonate;
390 parts of 2-phenoxyethyl methacrylate;
0.21 part of lauroyl peroxide;
2.9 parts of azobisisobutyronitrile;
5.4 parts of azobisisovaleronitrile;
7.1 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;
6.7 parts of N-methylmaleimide;
0.42 part of sodium hypophosphite;
the mass ratio is 2:1 of 31 parts of a copolyether of ethylene oxide and propylene oxide;
0.5 part of graphene oxide;
15.83 parts of super concentrated emulsifier;
3.5 parts of hexadecane;
0.7 part of polyvinyl alcohol;
8.4 parts of sodium methoxide;
17.6 parts of 30 percent sodium hydroxide solution;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) directly adding 3.7 parts of water, 2.8 parts of sodium vinylsulfonate, 8.7 parts of 2-ethylhexyl (meth) acrylate, 0.21 part of lauroyl peroxide and 0.42 part of sodium hypophosphite into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2 hours at 70 ℃, preserving heat for 2 hours, and cooling to obtain a super-concentrated emulsifier;
2) 12 parts of sodium styrene sulfonate, 390 parts of 2-phenoxyethyl methacrylate, 7.1 parts of maleic anhydride hydroxyethyl dimethacrylate and 31 parts of styrene dianhydride in a mass ratio of 2:1, adding ethylene oxide-propylene oxide copolyether, 0.5 part of graphene oxide and 6.7 parts of N-methylmaleimide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 8.4 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 9 parts of deionized water, 15.83 parts of prepared super-concentrated emulsifier, 3.5 parts of hexadecane and 0.7 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 13 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 4 minutes at the speed of 900 revolutions per minute;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 65 ℃ 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 5.4 parts of azobisisovaleronitrile;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 17.6 parts of 30% solubility sodium hydroxide solution, and replenishing water until the mass of the total solution is 1000 parts, thereby preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Example 2
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
2.8 parts of sodium vinylsulfonate;
8.7 parts of n-butyl (meth) acrylate;
12 parts of sodium methallyl sulfonate;
390 parts of 2-methacryloyloxyethyl ester;
0.21 part of lauroyl peroxide;
2.9 parts of dimethyl azodiisobutyrate;
5.4 parts of azobisisovaleronitrile;
7.1 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;
6.7 parts of 1-allyl-2-fluorobenzene;
0.42 part of sodium hypophosphite;
the mass ratio is 2:1 of 31 parts of a copolyether of ethylene oxide and propylene oxide;
0.5 part of graphene oxide;
15.83 parts of super concentrated emulsifier;
3.5 parts of hexadecane;
0.7 part of polyvinyl alcohol;
8.4 parts of sodium methoxide;
17.6 parts of 30 percent sodium hydroxide solution;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) 3.7 parts of water, 2.8 parts of sodium vinylsulfonate, 8.7 parts of n-butyl (methyl) acrylate, 0.21 part of lauroyl peroxide and 0.42 part of sodium hypophosphite are directly added into a three-neck flask with a stirring device, and after uniform stirring, the mixture is reacted for 2 hours at the temperature of 70 ℃, and then is kept warm for 2 hours, and is cooled to obtain the super-concentrated emulsifier.
2) 12 parts of sodium methallyl sulfonate, 390 parts of 2-methacryloyloxyethyl ester, 7.1 parts of maleic anhydride hydroxyethyl dimethacrylate and 31 parts of 2:1, adding ethylene oxide and propylene oxide copolyether, 0.5 part of graphene oxide and 6.7 parts of 1-allyl-2-fluorobenzene into a three-neck flask provided with a stirring device and a condensation reflux device, adding 8.4 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 9 parts of deionized water, 15.83 parts of prepared super-concentrated emulsifier, 3.5 parts of hexadecane and 0.7 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 13 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 4 minutes at the speed of 900 revolutions per minute;
6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 65 ℃ 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 dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 5.4 parts of azodiisovaleronitrile;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 17.6 parts of 30% solubility sodium hydroxide solution, and replenishing water until the mass of the total solution is 1000 parts, thereby preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Example 3
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
5.1 parts of sodium propenyl sulfonate;
9.2 parts of isobutyl (meth) acrylate;
7 parts of 2-acrylamide-2-methylpropanesulfonic acid;
420 parts of 2-propylheptyl acrylate;
0.43 part of tert-butyl peroxypivalate;
3.6 parts of azodiisobutyric acid;
6.2 parts of azodicyano valeric acid;
5.3 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester;
4.5 parts of N-ethylmaleimide;
0.61 part of sodium hypophosphite;
the mass ratio is 3:2 of 22 parts of a copolyether of ethylene oxide and propylene oxide;
0.9 part of graphene oxide;
21.04 parts of super concentrated emulsifier;
1.5 parts of hexadecanol;
0.3 part of polyvinylpyrrolidone;
5.5 parts of sodium ethoxide;
10.4 parts of potassium hydroxide;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) directly adding 5.7 parts of water, 5.1 parts of sodium propenyl sulfonate, 9.2 parts of isobutyl (methyl) acrylate, 0.43 part of tert-butyl peroxypivalate and 0.61 part of sodium hypophosphite into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1 hour at 75 ℃, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.
2) 7 parts of 2-acrylamide-2-methylpropanesulfonic acid, 420 parts of 2-propylheptyl acrylate, 5.3 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and 22 parts of a mixture of 3:2, adding ethylene oxide and propylene oxide copolyether, 0.9 part of graphene oxide and 4.5 parts of N-ethylmaleimide into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.5 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 20 parts of deionized water, 21.04 parts of the prepared super-concentrated emulsifier, 1.5 parts of hexadecanol and 0.3 part of polyvinylpyrrolidone into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 2.5 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 18 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 4 minutes at the speed of 1100 r/min;
6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 78 ℃ water bath at constant temperature for 7 hours, firstly dropwise adding the solution A for 5 hours, and then dropwise adding the solution B for 2 hours, wherein the solution A comprises 50 parts of water and 3.6 parts of azobisisobutyric acid, and the solution B comprises 50 parts of water and 6.2 parts of azobiscyanovaleric acid;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 10.4 parts of potassium hydroxide, and replenishing water until the mass of the total solution is 1000 parts, thereby preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Example 4
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
5.1 parts of a composition of sodium vinyl sulfonate and sodium propenyl sulfonate with the mass ratio of 3: 2;
9.2 parts of a composition of 2-ethylhexyl (meth) acrylate and benzyl methacrylate in a mass ratio of 1: 3;
7 parts of a composition of sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid in a mass ratio of 2: 1;
420 parts of a composition of 2-propylheptyl acrylate and 2-methacryloyloxyethyl ester in a mass ratio of 1: 1;
0.43 part of composition of lauroyl peroxide and dicyclohexyl peroxydicarbonate in a mass ratio of 1: 1;
3.6 parts of a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 2: 3;
6.2 parts of a composition of azobiscyanovaleric acid and azobisisoheptonitrile in a mass ratio of 1: 1;
5.3 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 3: 2;
4.5 parts of a composition of 1, 4-divinyl-2-azepane and 2-aminostyrene in a mass ratio of 2: 1;
0.61 part of sodium hypophosphite;
the mass ratio is 2: 22 parts of copolyether of ethylene oxide and propylene oxide of 1;
0.9 part of graphene oxide;
21.04 parts of super concentrated emulsifier;
1.5 parts of a composition of cetyl alcohol and lauryl methacrylate in a mass ratio of 1: 4;
0.3 part of a composition of polyvinyl alcohol and polyvinylpyrrolidone in a mass ratio of 1: 1;
5.5 parts of a composition of sodium ethoxide and triisopropanolamine in a mass ratio of 1: 2;
10.4 parts of a composition of sodium carbonate and potassium carbonate in a mass ratio of 4: 1;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) 5.7 parts of water, 5.1 parts of a composition of sodium vinyl sulfonate and sodium propenyl sulfonate in a mass ratio of 3:2, 9.2 parts of a composition of 2-ethylhexyl (meth) acrylate and benzyl methacrylate in a mass ratio of 1:3, 0.43 part of a composition of lauroyl peroxide and dicyclohexyl peroxydicarbonate in a mass ratio of 1:1 and 0.61 part of sodium hypophosphite are directly added into a three-neck flask with a stirring device, the mixture is uniformly stirred, the temperature is controlled to be 75 ℃ for reaction for 1 hour, the temperature is maintained for 1 hour, and the reaction is cooled to obtain the super-concentrated emulsifier.
2) 7 parts of a composition of sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid in a mass ratio of 2:1, 420 parts of a composition of 2-propylheptyl acrylate and 2-methacryloyloxyethyl ester in a mass ratio of 1:1, 5.3 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 3:2, 22 parts of a composition of 2:1, adding a composition of ethylene oxide and propylene oxide copolyether, 0.9 part of graphene oxide and 4.5 parts of 1, 4-divinyl-2-azepin and 2-aminostyrene in a mass ratio of 2:1 into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.5 parts of a composition of sodium ethoxide and triisopropanolamine in a mass ratio of 1:2, adjusting the pH to 8-8.5, and uniformly stirring to obtain a reaction monomer mixed solution;
3) adding 20 parts of deionized water, 21.04 parts of the prepared super concentrated emulsifier, 1.5 parts of a composition of cetyl alcohol and lauryl methacrylate in a mass ratio of 1:4 and 0.3 part of a composition of polyvinyl alcohol and polyvinylpyrrolidone 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 1.5 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 18 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 4 minutes at the speed of 1100 r/min;
6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 78 ℃ water bath at a constant temperature for 7 hours, dropwise adding the solution A for 5 hours, and dropwise adding the solution B for 2 hours, wherein the solution A comprises 50 parts of water and 3.6 parts of a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 2:3, and the solution B comprises 50 parts of water and 6.2 parts of a composition of azobiscyanovaleric acid and azobisisoheptonitrile in a mass ratio of 1: 1;
7) after the reaction is finished, preserving heat, curing for 1 hour, cooling, adding 10.4 parts of a composition of sodium carbonate and potassium carbonate in a mass ratio of 4:1, and replenishing water until the mass of the total solution is 1000 parts, thus preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Example 5
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
3.5 parts of sodium vinylsulfonate;
6.4 parts of benzyl methacrylate;
19 parts of 2-acrylamide-2-methylpropanesulfonic acid;
400 parts of 2-methacryloyloxyethyl ester;
0.15 part of dicyclohexyl peroxydicarbonate;
5.2 parts of dimethyl azodiisobutyrate;
4.6 parts of azobisisoheptonitrile;
8.3 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;
5.2 parts of 1-vinyl-2, 5-pyrrolidine diketone;
0.27 part of sodium hypophosphite;
the mass ratio is 1: 28 parts of copolyether of ethylene oxide and propylene oxide of 1;
0.1 part of graphene oxide;
12.82 parts of super concentrated emulsifier;
4.5 parts of octadecyl acrylate;
0.9 part of hydroxypropyl cellulose;
5.7 parts of ethanolamine;
12.3 parts of sodium bicarbonate;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) 2.5 parts of water, 3.5 parts of sodium vinylsulfonate, 6.4 parts of benzyl methacrylate, 0.15 part of dicyclohexyl peroxydicarbonate and 0.27 part of sodium hypophosphite are directly added into a three-neck flask with a stirring device, after uniform stirring, the temperature is controlled to be 80 ℃ for reaction for 1.5 hours, then the temperature is kept for 1 hour, and the ultra-concentrated emulsifier is obtained after cooling.
2) 19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 400 parts of 2-methacryloyloxyethyl ester, 8.3 parts of maleic anhydride hydroxyethyl dimethacrylate and 28 parts of a mixture of 1:1, adding ethylene oxide and propylene oxide copolyether, 0.1 part of graphene oxide and 5.2 parts of 1-vinyl-2, 5-pyrrolidine dione 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 8-20 parts of deionized water, 12.82 parts of prepared super-concentrated emulsifier, 4.5 parts of octadecyl acrylate and 0.9 part of hydroxypropyl cellulose into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 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 for 2 hours, and continuously stirring for 17 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 2 minutes at the speed of 1150 revolutions per minute;
6) placing the centrifuged ultra-concentrated emulsion-containing centrifugal test tube in a 69 ℃ 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 5.2 parts of dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 4.6 parts of azodiisoheptonitrile;
7) after the reaction is finished, preserving heat, curing for 2 hours, cooling, adding 12.3 parts of sodium bicarbonate, and replenishing water until the mass of the total solution is 1000 parts, thereby preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Example 6
The raw materials for preparing the high-performance super-concentrated emulsion polymer comprise the following components in parts by mass of 1000:
3.5 parts of sodium propenyl sulfonate;
6.4 parts of octadecyl (meth) acrylate;
19 parts of 2-acrylamide-2-methylpropanesulfonic acid;
400 parts of 2-methacryloyloxyethyl ester;
0.15 part of dicyclohexyl peroxydicarbonate;
5.2 parts of a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 2: 3;
4.6 parts of azobisisoheptonitrile;
8.3 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 3: 2;
5.2 parts of 1-allyl-4-fluorobenzene;
0.27 part of sodium hypophosphite;
the mass ratio is 1: 28 parts of copolyether of ethylene oxide and propylene oxide of 1;
0.1 part of graphene oxide;
12.82 parts of super concentrated emulsifier;
4.5 parts of lauryl methacrylate;
0.9 part of hydroxypropyl cellulose;
5.7 parts of ethanolamine;
12.3 parts of sodium bicarbonate;
the balance of water.
The total mass portion is 1000, and the solid content is 50%.
The preparation method comprises the following steps:
1) 2.5 parts of water, 3.5 parts of sodium propenyl sulfonate, 6.4 parts of octadecyl (methyl) acrylate, 0.15 part of dicyclohexyl peroxydicarbonate and 0.27 part of sodium hypophosphite are directly added into a three-neck flask with a stirring device, after uniform stirring, the temperature is controlled to be 80 ℃ for reaction for 1.5 hours, then the temperature is kept for 1 hour, and the ultra-concentrated emulsifier is obtained after cooling.
2) 19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 400 parts of 2-methacryloxyethyl ester, 8.3 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloxyethyl) pyromellitic dianhydride ester in a mass ratio of 3:2, 28 parts of a mixture of 1:1, adding ethylene oxide and propylene oxide copolyether, 0.1 part of graphene oxide and 5.2 parts of 1-allyl-4-fluorobenzene 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 8-20 parts of deionized water, 12.82 parts of prepared super-concentrated emulsifier, 4.5 parts of lauryl methacrylate and 0.9 part of hydroxypropyl cellulose into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 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 for 2 hours, and continuously stirring for 17 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 2 minutes at the speed of 1150 revolutions per minute;
6) placing the centrifuged ultra-concentrated emulsion-containing centrifugal test tube in a 69 ℃ 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 5.2 parts of a composition of azodiisobutyronitrile and azodiisobutyronitrile in a mass ratio of 2:3, and the solution B comprises 50 parts of water and 4.6 parts of azodiisoheptonitrile;
7) after the reaction is finished, preserving heat, curing for 2 hours, cooling, adding 12.3 parts of sodium bicarbonate, and replenishing water until the mass of the total solution is 1000 parts, thereby preparing the sulfonic ester-based polymer with the mass fraction of 50%.
Performance test Table for products of examples
As can be seen from the above table, the sulfonic ester based super emulsion polymer waterproof coating of the present invention has excellent properties required by the market, and the properties thereof are superior to those of the conventional waterproof coating. The combination of example 4 shows the excellent performance of the invention, stable property, long service life, good ductility, high tensile strength, wear resistance, impact resistance, no sticky back and high wet surface bonding strength. The waterproof paint is suitable for waterproofing the surfaces of concrete buildings in various environments, has simple and convenient preparation method and 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 a high-performance super-concentrated emulsion polymer is characterized by comprising the following steps:
1) directly adding 2.5-6.0 parts of water, 2.3-5.5 parts of hydrophilic small monomer for emulsification, 5.4-9.2 parts of hydrophobic small monomer for emulsification, 0.10-0.45 part of emulsion initiator and 0.21-0.62 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 a super-concentrated emulsifier;
the hydrophilic small monomer for emulsification is a sulfonic hydrophilic monomer, and is one or two of sodium vinyl sulfonate and sodium propenyl sulfonate;
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;
the chain transfer agent is sodium hypophosphite;
2) adding 5-19 parts of sulfonic hydrophilic small monomer, 390-445 parts of ester hydrophobic small monomer, 4.7-8.9 parts of cross-linking agent, 19-40 parts of polyether, 0.1-0.9 part of graphene oxide and 3.9-8.5 parts of rigid small monomer into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.5-9.7 parts of pH regulator to adjust the pH value to 8-8.5, and uniformly stirring;
the sulfonic hydrophilic monomer is one or more of sodium methallyl sulfonate, sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid;
one or more of ester group hydrophobic monomer 2-phenoxyethyl methacrylate, 2-propylheptyl acrylate, methacryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl ester and methacryloyloxyethyl hexahydrophthalate monoester;
3) adding 8-20 parts of deionized water, 10.51-21.77 parts of prepared super-concentrated emulsifier, 1.0-4.5 parts of co-emulsifier and 0.2-0.9 part 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 65-85 ℃ for 6-8 hours at constant temperature, firstly dripping the solution A for 5-6 hours, and then dripping the solution B for 1-2 hours, wherein the solution A comprises 50 parts of water and 2.5-5.3 parts of initiator a, and the solution B comprises 50 parts of water and 4.1-6.6 parts of initiator B;
7) after the reaction is finished, preserving heat, curing for 1-2 hours, cooling, adding 9.7-20.6 parts of neutralizing agent, and supplementing water until the mass part of the total solution is 1000 parts, thus obtaining the aqueous solution.
2. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the auxiliary emulsifier is one or more of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate.
3. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the liquid film reinforcing agent is one or more of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose.
4. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the emulsion initiator is one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate.
5. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: 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.
6. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the cross-linking agent is one or two of pyromellitic dianhydride hydroxyethyl dimethacrylate and di (methacryloyloxyethyl) pyromellitic dianhydride ester.
7. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: 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.
8. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the rigid small monomer is one or more of N-methylmaleimide, N-ethylmaleimide, 1-vinyl-2, 5-pyrrolidinedione, 1, 4-divinyl-2-azepane, 3-methyl-1-vinyl-2-azepane, (4-methylphenyl) azomethine, 1-phenyl vinyl boric acid, 4-methoxy-2-vinylaniline, 2-aminostyrene, (4-methylphenyl) azomethine, N- (4-vinylbenzyl) -N, N-dimethylamine, 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene.
9. The method of preparing a high performance superconcentrated emulsion polymer of claim 1, wherein: the neutralizer is one or more of 30% solubility sodium hydroxide solution, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate; the pH regulator is one or more of sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.
10. A high performance superconcentrated emulsion polymer characterized by: prepared by the method of any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831300A (en) * | 2021-01-29 | 2021-05-25 | 湖北工业大学 | Adhesive for high-efficiency resin material and preparation method thereof |
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