阅读说明：本技术 一种耐高温型酰胺烷基超浓乳液聚合物制备方法 (Preparation method of high-temperature-resistant amidoalkyl super-concentrated emulsion polymer ) 是由 柯凯 姚恒 罗人豪 于 2019-09-19 设计创作，主要内容包括：本发明公开了一种耐高温型酰胺烷基超浓乳液聚合物制备方法,所述聚合物主要由以下几种材料制备而成：乳化用亲水小单体1.5-3.0份、乳化用疏水小单体2.5-3.5份、酰胺小单体10-35份、乳液引发剂0.04-0.18份、引发剂a 2.5-4.9份、引发剂b 3.3-5.6份、烷基小单体380-420份、交联剂6.6-8.9份、柔性小单体4.5-7.2份、氟功能单体25-42份、链转移剂0.08-0.30份、中和剂5-10份、pH调节剂5-10份、助乳化剂3.0-9.0份、液膜增强剂0.6-1.8份,其余为水,总质量份数为1000,固含为50％。本发明以酰胺小单体和烷基小单体采用超浓乳液聚合法聚合而成,使用超浓乳液聚合法,配制出了胶冻状的超浓乳液进行聚合反应,超浓乳液有着稳定性好的特点,形成的超浓乳液聚合物也有着非常优秀的稳定性。(The invention discloses a preparation method of a high-temperature resistant amidoalkyl super-concentrated emulsion polymer, which is mainly prepared from the following materials: 1.5-3.0 parts of hydrophilic small monomer for emulsification, 2.5-3.5 parts of hydrophobic small monomer for emulsification, 10-35 parts of amide small monomer, 0.04-0.18 part of emulsion initiator, 2.5-4.9 parts of initiator a, 3.3-5.6 parts of initiator b, 420 parts of alkyl small monomer 380-doped, 6.6-8.9 parts of cross-linking agent, 4.5-7.2 parts of flexible small monomer, 25-42 parts of fluorine functional monomer, 0.08-0.30 part of chain transfer agent, 5-10 parts of neutralizing agent, 5-10 parts of pH regulator, 3.0-9.0 parts of auxiliary emulsifier, 0.6-1.8 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 invention is polymerized by amide small monomers and alkyl small monomers by adopting a super-concentrated emulsion polymerization method, and a jelly-like super-concentrated emulsion is prepared by using the super-concentrated emulsion polymerization method for polymerization reaction, and the super-concentrated emulsion has the characteristic of good stability, and the formed super-concentrated emulsion polymer also has very excellent stability.)

1. A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer is characterized by comprising the following steps:

directly adding 3.0-5.0 parts of water, 1.5-3.0 parts of hydrophilic small monomer for emulsification, 2.5-3.5 parts of hydrophobic small monomer for emulsification, 0.04-0.18 part of emulsion initiator and 0.08-0.30 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1-1.5 hours at 70-90 ℃, preserving heat for 1-1.5 hours, and cooling to obtain the super-concentrated emulsifier; the hydrophobic small monomer for emulsification is N-octadecyl acrylamide and/or octadecyl vinyl ether;

step (2) adding 10-35 parts of amide hydrophilic small monomer, 380-420 parts of alkyl hydrophobic small monomer, 6.6-8.9 parts of cross-linking agent, 25-42 parts of fluorine functional monomer and 4.5-7.2 parts of flexible small monomer 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 9-9.5, and uniformly stirring to obtain a reaction monomer mixed solution; the alkyl hydrophobic monomer is N-octadecyl acrylamide and/or octadecyl vinyl ether; the cross-linking agent is pyromellitic dianhydride hydroxyethyl dimethacrylate and/or bis (methacryloyloxyethyl) pyromellitic dianhydride ester;

step (3) adding 5-16 parts of deionized water, 7.12-11.98 parts of the super-concentrated emulsifier prepared in step (1), 3.0-9.0 parts of co-emulsifier and 0.6-1.8 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;

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 obtain super-concentrated emulsion;

step (5) at room temperature, transferring the super-concentrated emulsion into a centrifugal test tube, and centrifuging for 2-4 minutes at the speed of 900-;

step (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 2.5-4.9 parts of initiator a, the solution B comprises 50 parts of water and 3.3-5.6 parts of initiator B, and the initiation rate of the initiator B is higher than that of the initiator a;

and (4) after the reaction in the step (7) is finished, preserving heat, curing for 1-2 hours, adding 5-10 parts of neutralizing agent, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer.

2. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (1), the hydrophilic small monomer for emulsification is any one or a combination of more of acrylamide, 4- (acrylamide) benzoic acid, 2-acrylamide phenylboronic acid, 4-vinylbenzamide, cinnamamide, (4-vinylbenzene) sulfonamide, N-dimethylacrylamide and N, N-dimethyl methacrylamide.

3. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (2), the amide hydrophilic small monomer is any one or a combination of several of acrylamide, 4- (acrylamide) benzoic acid, 2-acrylamide phenylboronic acid, 4-vinylbenzamide, cinnamamide, (4-vinylbenzene) sulfonamide, N-dimethylacrylamide and N, N-dimethylmethacrylamide.

4. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (1), the emulsion initiator is any one or a combination of more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate.

5. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (6), the initiator a is any one or a combination of a plurality of azodiisobutyronitriles, azodiisobutyronitriles and dimethyl azodiisobutyrate.

6. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (6), the initiator b is any one or a combination of a plurality of azo diisovaleronitrile, azo dicyano valeric acid and azo diisoheptanonitrile.

7. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (3), the coemulsifier is any one or a combination of more of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate.

8. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (3), the liquid film reinforcing agent is any one or a combination of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose.

9. The method for preparing high temperature resistant amidoalkyl super emulsion polymer as claimed in claim 1, wherein: in the step (2), the flexible small monomer is any one or a combination of more of 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 4-diaminodiphenyl ether, cyclobutane tetracarboxylic dianhydride, diaminododecylbenzene and diaminooctadecylbenzene.

10. A high-temperature resistant amido alkyl super-concentrated emulsion polymer is characterized in that: made by the process of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of building materials, relates to the field of waterproof materials, and particularly relates to a preparation method of a high-temperature-resistant amidoalkyl super-concentrated emulsion polymer.

Background

The synthesis reaction of the polymer emulsion is a polymerization process of preparing an emulsion from monomers and water under the action of an emulsifier. The synthesis of the polymer emulsion belongs to one of more strict synthesis modes, before the polymer emulsion is produced in a large scale, a strict pilot test needs to be carried out, particularly, the requirement of the thermally-initiated polymer emulsion synthesis experiment on temperature control is higher, and under the non-automatic operation condition, the influence of human factors inevitably influences the reaction process of the pilot synthesis, such as the dripping time and the dripping speed of a pre-emulsified monomer, the control of the temperature in a reaction kettle, the deviation of the synthesis process caused by the temperature difference between the upper layer liquid and the lower layer liquid of the emulsion and the like.

The invention adopts the super-concentrated emulsion polymerization method to prepare the polymer emulsion, can simply and conveniently control the reaction conditions and is convenient for the implementation and operation of various occasions. The super-concentrated emulsion polymerization has good application prospect, and can be directly used for preparing hydrophobic-hydrophilic (or hydrophilic-hydrophobic) composite polymer permeable membranes besides preparing high-solid-content latex. In addition, the super-concentrated emulsion polymerization can also be used for preparing high molecular weight monodisperse polymer latex particles, and can be widely used in the fields of physics, chemistry, medicine, biology and the like.

Patent CN02105398.7 discloses a polymer emulsion having good film structure characteristics, which is prepared by mixing a synthetic polymer emulsion containing polymer particles with a diameter of 0.15 μm or more and a synthetic polymer emulsion containing polymer particles with a diameter of 0.10 μm or less, wherein the latter has a glass transition temperature at least 20 degrees lower than that of the former and a particle size ratio of 2 or more between the former and the latter, and is used for manufacturing waterproof paper and/or recycled paper.

Patent CN201780012686.8 discloses a modified polymer and a stable emulsion comprising the same, the present invention discloses a modified polymer comprising a diene-based polymer chain and at least one terminal end terminated with a blocked isocyanate group. The blocked isocyanate group may be the reaction product of an isocyanate and a blocking agent, and the blocking agent is selected such that the modified polymer is deblocked at a temperature of at least 100 ℃. An aqueous emulsion of the modified polymer may be provided which may be free of surfactant. The emulsion may be combined with one or more latexes to provide a treatment solution for fabrics or fibers that does not require the use of resorcinol and formaldehyde. Once treated and dried, the fabric or fiber can be used to impart tensile strength to rubber products such as tires, air springs, flexible couplings, power transmission belts, conveyor belts, and fluid transfer hoses.

The patent CN108753151A discloses an acrylic acid waterproof coating, and the invention discloses an acrylic acid waterproof coating. 5-15 parts of acrylic emulsion, 20 parts of acrylic ester elastic emulsion, 10-25 parts of polyurethane modified acrylic ester waterproof emulsion, 1-5 parts of organosilicon waterproofing agent, 0.5-3 parts of silicon dioxide, 20-40 parts of pigment and filler, 0-0.5 part of sterilization preservative, 0-1 part of anti-aging agent, 0.2-0.8 part of dispersing agent, 0.4-1 part of defoaming agent, 0.5-2 parts of film-forming auxiliary agent, 0.6-3 parts of hydroxyethyl cellulose, 0.3-1 part of ammonium metavanadate and 10-30 parts of water. The invention has excellent high elasticity and excellent waterproof performance. The product is nontoxic, tasteless, safe and environment-friendly. The coating has strong water resistance, alkali resistance and ultraviolet resistance, and has higher elongation at break, tensile strength and automatic repair function.

However, products in the prior art are only improved on one aspect, and the comprehensive performance is difficult to achieve the effects of excellent stain resistance, heat resistance, tensile strength and water resistance, so that a waterproof coating with more excellent performance needs to be further developed on the basis of the prior art.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of an amidoalkyl super-concentrated emulsion polymer.

The invention uses a super-concentrated emulsion method to synthesize an amidoalkyl super-concentrated emulsion polymer. The invention prepares a macromolecular material containing amidoalkyl by a super-concentrated emulsion method. The polymer utilizes hydrophilic and hydrophobic small monomers to carry out polymerization reaction under the action of an initiator, and the initiator is added in a dropwise manner, so that the reaction can be carried out more fully, and the polymer product is more stable.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer is characterized by comprising the following steps:

directly adding 3.0-5.0 parts of water, 1.5-3.0 parts of hydrophilic small monomer for emulsification, 2.5-3.5 parts of hydrophobic small monomer for emulsification, 0.04-0.18 part of emulsion initiator and 0.08-0.30 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1-1.5 hours at 70-90 ℃, preserving heat for 1-1.5 hours, and cooling to obtain the super-concentrated emulsifier; the hydrophobic small monomer for emulsification is N-octadecyl acrylamide and/or octadecyl vinyl ether;

step (2) adding 10-35 parts of amide hydrophilic small monomer, 380-420 parts of alkyl hydrophobic small monomer, 6.6-8.9 parts of cross-linking agent, 25-42 parts of fluorine functional monomer and 4.5-7.2 parts of flexible small monomer 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 9-9.5, and uniformly stirring to obtain a reaction monomer mixed solution; the alkyl hydrophobic monomer is N-octadecyl acrylamide and/or octadecyl vinyl ether; the cross-linking agent is pyromellitic dianhydride hydroxyethyl dimethacrylate and/or bis (methacryloyloxyethyl) pyromellitic dianhydride ester;

step (3) adding 5-16 parts of deionized water, 7.12-11.98 parts of the super-concentrated emulsifier prepared in step (1), 3.0-9.0 parts of co-emulsifier and 0.6-1.8 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;

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 obtain super-concentrated emulsion;

step (5) at room temperature, transferring the super-concentrated emulsion into a centrifugal test tube, and centrifuging for 2-4 minutes at the speed of 900-;

step (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 2.5-4.9 parts of initiator a, the solution B comprises 50 parts of water and 3.3-5.6 parts of initiator B, and the initiation rate of the initiator B is higher than that of the initiator a;

and (4) after the reaction in the step (7) is finished, preserving heat, curing for 1-2 hours, adding 5-10 parts of neutralizing agent, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer.

Preferably, in the step (1), the small hydrophilic monomer for emulsification is any one or a combination of several of acrylamide, 4- (acrylamide) benzoic acid, 2-acrylamide phenylboronic acid, 4-vinylbenzamide, cinnamamide, (4-vinylbenzene) sulfonamide, N-dimethylacrylamide and N, N-dimethylmethacrylamide.

Preferably, in the step (2), the amide hydrophilic small monomer is any one or a combination of several of acrylamide, 4- (acrylamide) benzoic acid, 2-acrylamide phenylboronic acid, 4-vinylbenzamide, cinnamamide, (4-vinylbenzene) sulfonamide, N-dimethylacrylamide and N, N-dimethylmethacrylamide.

Preferably, in the step (1), the emulsion initiator is any one or a combination of more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate.

Preferably, in the step (6), the initiator a is any one or combination of azodiisobutyronitrile, azodiisobutyronitrile and dimethyl azodiisobutyrate.

Preferably, in the step (6), the initiator b is any one or a combination of several of azobisisovaleronitrile, azobiscyanovaleric acid and azobisisoheptonitrile.

Preferably, in the step (3), the coemulsifier is any one or a combination of hexadecane, hexadecanol, stearyl methacrylate, stearyl acrylate and lauryl methacrylate.

Preferably, in the step (3), the liquid film enhancer is any one or a combination of polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose.

Preferably, in the step (2), the flexible small monomer is any one or a combination of more of 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 4-diaminodiphenyl ether, cyclobutane tetracarboxylic dianhydride, diaminododecylbenzene and diaminooctadecylbenzene.

Preferably, in the step (7), the neutralizer is any one or a combination of several of sodium hydroxide solution with 30% solubility, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate.

Preferably, in the step (2), the pH regulator is any one or a combination of several of sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.

The preparation method of the amide alkyl super concentrated emulsion polymer mainly comprises the following components:

1.5-3.0 parts of hydrophilic small monomer for emulsification;

2.5-3.5 parts of hydrophobic small monomer for emulsification;

10-35 parts of amide hydrophilic small monomer;

380-420 parts of alkyl hydrophobic small monomer;

0.04-0.18 part of emulsion initiator;

2.5-4.9 parts of an initiator a;

3.3-5.6 parts of an initiator b;

6.6-8.9 parts of a cross-linking agent;

4.5-7.2 parts of flexible small monomer;

0.08-0.30 part of chain transfer agent;

7.12-11.98 parts of super-concentrated emulsifier;

3.0-9.0 parts of auxiliary emulsifier;

0.6-1.8 parts of liquid film intensifier;

25-42 parts of a fluorine functional monomer;

5-10 parts of a pH regulator;

5-10 parts of a neutralizing agent;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The invention has the advantages of

The polymer of the invention adopts a super-concentrated emulsion polymerization method to synthesize the amide alkyl emulsion polymer. The method mixes the polymer monomer and the super-concentrated emulsifier to prepare the super-concentrated emulsion, and then utilizes the super-concentrated emulsion to carry out emulsion polymerization reaction. The polymer emulsion is formed by polymerizing the hydrophobic small monomer and the hydrophilic small monomer, has excellent waterproof performance, can be applied to various fields, and has the following advantages:

1. the invention uses super-concentrated emulsion polymerization to prepare amide alkyl super-concentrated emulsion polymer, and a large amount of alkyl hydrophobic small monomers ensure that the invention has excellent waterproof performance.

2. The invention uses the super-concentrated emulsion polymerization method to prepare the jelly-like super-concentrated emulsion for polymerization reaction, the super-concentrated emulsion has the characteristic of good stability, and the formed super-concentrated emulsion polymer also has very excellent stability.

3. The invention combines the advantages of a super-concentrated emulsion polymerization method and a soap-free emulsion polymerization method, and utilizes the reaction monomers to prepare the super-concentrated emulsifier which has the function similar to that of a conventional emulsifier, thereby saving the reaction cost.

4. The initiator with shorter half-life period is used in the process of preparing the super-concentrated emulsifier, and the initiation rate of the initiator is higher, so that the synthesis rate of the super-concentrated emulsifier is increased, and the reaction time is saved.

5. The initiator with weak initiation activity is used in the early stage of the reaction with high polymerization reaction rate, so that the cost is saved; the initiator with stronger initiating activity is used in the later stage of slower polymerization reaction rate, so that the polymerization reaction is accelerated, and the time is saved.

6. The invention adopts the fluorine functional monomer, enhances the defoaming capability of the emulsion, ensures that the reaction is not interfered by bubbles, increases the reaction rate, and forms a polymer coating film which is smoother and has more excellent waterproof effect.

Detailed Description

The present invention is further illustrated by the following examples, which are only for explaining the present invention and are not intended to limit the contents, and in the examples of the present invention, the hydrophilic small monomers for emulsification in step (1) and the hydrophilic small amide monomers in step (2) are selected on the basis that the activity of the hydrophilic small monomers for emulsification is smaller than that of the hydrophilic small amide monomers in step (2).

Example 1

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

1.5 parts of cinnamamide;

2.5 parts of N-octadecyl acrylamide;

12 parts of acrylamide;

420 parts of octadecyl vinyl ether;

0.05 part of composition of lauroyl peroxide and tert-butyl peroxypivalate with the mass ratio of 1: 1;

2.7 parts of dimethyl azodiisobutyrate;

3.9 parts of azodicyano valeric acid;

6.7 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;

4.6 parts of cyclobutane tetracarboxylic dianhydride;

0.10 part of sodium methallyl sulfonate;

7.15 parts of super concentrated emulsifier;

3.0 parts of octadecyl acrylate;

0.6 part of polyvinyl alcohol;

30 parts of perfluorooctyl ethyl acrylate;

6.6 parts of diethanolamine;

5.8 parts of sodium carbonate;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The preparation process of the high-temperature resistant amido alkyl super-concentrated emulsion polymer comprises the following steps:

1) directly adding 3.0 parts of water, 1.5 parts of cinnamamide, 2.5 parts of N-octadecyl acrylamide, 0.05 part of a composition of lauroyl peroxide and tert-butyl peroxypivalate with the mass ratio of 1:1 and 0.10 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 70 ℃, preserving the temperature for 1 hour, and cooling to obtain the super-concentrated emulsifier.

2) Adding 12 parts of acrylamide, 420 parts of octadecyl vinyl ether, 6.7 parts of maleic anhydride hydroxyethyl dimethacrylate, 30 parts of perfluorooctyl ethyl acrylate and 4.6 parts of cyclobutane tetracarboxylic dianhydride into a three-neck flask provided with a stirring device and a condensation reflux device, adding 6.6 parts of diethanolamine to adjust the pH value to 9-9.5, and uniformly stirring to prepare a reaction monomer mixed solution;

3) adding 6 parts of deionized water, 7.15 parts of the super-concentrated emulsifier prepared in the step (1), 3.0 parts of octadecyl acrylate and 0.6 part of polyvinyl alcohol into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 1 hour 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 11 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 950 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 7 hours, and then dripping the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 2.7 parts of dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 3.9 parts of azodicyan valeric acid;

7) after the reaction is finished, preserving heat, curing for 2 hours, adding 5.8 parts of sodium carbonate, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

Example 2

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

2.3 parts of 4-vinylbenzamide;

octadecyl vinyl ether 3.1 parts;

30 parts of N, N-dimethylacrylamide;

400 parts of N-octadecyl acrylamide;

0.11 part of lauroyl peroxide;

3.2 parts of azobisisobutyronitrile;

4.6 parts of the composition of azodicyano valeric acid and azodiisoheptanonitrile in a mass ratio of 1: 1;

8.2 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester;

5.5 parts of diaminooctadecyl benzene;

0.16 part of sodium methallyl sulfonate;

9.27 parts of super concentrated emulsifier;

4.0 parts of octadecyl methacrylate;

0.8 part of hydroxypropyl cellulose;

26 parts of perfluorooctyl ethyl acrylate;

5.4 parts of triethanolamine;

6.7 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 3: 1;

the balance of water.

The total mass is 1000, and the solid content is 50%.

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer comprises the following specific preparation processes:

1) directly adding 3.6 parts of water, 2.3 parts of 4-vinylbenzamide, 3.1 parts of octadecyl vinyl ether, 0.11 part of lauroyl peroxide and 0.16 part of sodium methallylsulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1.5 hours at 75 ℃, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.

2) Adding 30 parts of N, N-dimethylacrylamide, 400 parts of N-octadecyl acrylamide, 8.2 parts of bis (methacryloyloxyethyl) phthalic anhydride ester, 26 parts of perfluorooctyl ethyl acrylate and 5.5 parts of diaminooctadecyl benzene into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.4 parts of triethanolamine, adjusting the pH value to 9-9.5, and uniformly stirring to prepare a reaction monomer mixed solution;

3) adding 14 parts of deionized water, 9.27 parts of the super-concentrated emulsifier prepared in the step (1), 4.0 parts of octadecyl methacrylate and 0.8 part 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 18 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 1000 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 comprises 50 parts of water and 3.2 parts of azobisisobutyronitrile, and the solution B comprises 50 parts of water and 4.6 parts of a composition of azobiscyanovaleric acid and azobisisoheptonitrile with the mass ratio of 1: 1;

7) after the reaction is finished, preserving heat, curing for 2 hours, adding 6.7 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 3:1, and replenishing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

Example 3

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

1.7 parts of (4-vinyl benzene) sulfonamide;

2.7 parts of N-octadecyl acrylamide;

25 parts of 2-acrylamide phenylboronic acid;

410 parts of octadecyl vinyl ether;

0.08 part of tert-butyl peroxypivalate;

4.3 parts of azodiisobutyric acid;

5.1 parts of azobisisoheptonitrile;

7.4 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;

6.2 parts of diamino dodecyl benzene;

0.12 part of sodium methallyl sulfonate;

8.80 parts of super concentrated emulsifier;

5.0 parts of hexadecane;

1.0 part of polyvinylpyrrolidone;

25 parts of trifluoroethyl acrylate;

5.9 parts of ethanolamine;

5.3 parts of 30 percent sodium hydroxide solution;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The preparation process of the high-temperature resistant amido alkyl super-concentrated emulsion polymer comprises the following steps:

1) 4.2 parts of water, 1.7 parts of (4-vinyl benzene) sulfamide, 2.7 parts of N-octadecyl acrylamide, 0.08 part of tert-butyl peroxypivalate and 0.12 part of sodium methallylsulfonate are directly added into a three-neck flask with a stirring device, after uniform stirring, the temperature is controlled at 82 ℃ for reaction for 1.5 hours, then the temperature is kept for 1.5 hours, and the super-concentrated emulsifier is obtained after cooling.

2) Adding 25 parts of 2-acrylamide phenylboronic acid, 410 parts of octadecyl vinyl ether, 7.4 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate, 25 parts of trifluoroethyl acrylate and 6.2 parts of diaminododecylbenzene into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.9 parts of ethanolamine to adjust the pH value to 9-9.5, and uniformly stirring to obtain a reaction monomer mixed solution;

3) adding 7 parts of deionized water, 8.80 parts of the super-concentrated emulsifier prepared in the step (1), 5.0 parts of hexadecane 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 for 2 hours, and continuously stirring for 14 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 1200 r/min;

6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 78 ℃ water bath at a constant temperature for 6 hours, 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 4.3 parts of azobisisobutyric acid, and the solution B comprises 50 parts of water and 5.1 parts of azobisisoheptonitrile;

7) after the reaction is finished, preserving heat, curing for 1 hour, adding 5.3 parts of 30% solubility sodium hydroxide solution, and supplementing water until the total solution mass is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

Example 4

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

2.8 parts of acrylamide;

3.2 parts of N-octadecyl acrylamide;

35 parts of (4-vinyl benzene) sulfonamide;

380 parts of octadecyl vinyl ether;

0.17 part of dicyclohexyl peroxydicarbonate;

4.0 parts of dimethyl azodiisobutyrate;

5.4 parts of azobisisovaleronitrile;

7.9 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate;

4.8 parts of 1, 2-bis (4-aminophenoxy) ethane;

0.22 part of sodium methallyl sulfonate;

11.29 parts of super concentrated emulsifier;

9.0 parts of lauryl methacrylate;

1.8 parts of polyvinylpyrrolidone;

34 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 3: 1;

6.2 parts of triethanolamine;

7.6 parts of potassium carbonate;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The preparation process of the high-temperature resistant amido alkyl super-concentrated emulsion polymer comprises the following steps:

1) 4.9 parts of water, 2.8 parts of acrylamide, 3.2 parts of N-octadecyl acrylamide, 0.17 part of dicyclohexyl peroxydicarbonate and 0.22 part of sodium methallylsulfonate are directly added into a three-neck flask with a stirring device, after uniform stirring, the temperature is controlled to be 88 ℃ for reaction for 1 hour, then the temperature is kept for 1 hour, and the ultra-concentrated emulsifier is obtained after cooling.

2) Adding 35 parts of (4-vinylbenzene) sulfonamide, 380 parts of octadecyl vinyl ether, 7.9 parts of pyromellitic dianhydride hydroxyethyl dimethacrylate, 34 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 3:1 and 4.8 parts of 1, 2-bis (4-aminophenoxy) ethane into a three-neck flask provided with a stirring device and a condensation reflux device, adding 6.2 parts of triethanolamine to adjust the pH value to 9-9.5, and uniformly stirring to prepare a reaction monomer mixed solution;

3) adding 16 parts of deionized water, 11.29 parts of the super-concentrated emulsifier prepared in the step (1), 9.0 parts of lauryl methacrylate and 1.8 parts of polyvinylpyrrolidone into a three-neck flask provided with a stirring device and a condensation reflux device, and stirring for 1 hour 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 11 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 1150 revolutions per minute;

6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 73 ℃ water bath, keeping the temperature constant for 7 hours, firstly dripping the solution A for 6 hours, and then dripping the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 4.0 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 2 hours, adding 7.6 parts of potassium carbonate, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

Example 5

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

3.0 parts of a composition of cinnamamide and (4-vinyl benzene) sulfamide in a mass ratio of 1: 1;

3.5 parts of a composition of N-octadecyl acrylamide and octadecyl vinyl ether in a mass ratio of 1: 1;

17 parts of a composition of 2-acrylamide phenylboronic acid and 4-vinylbenzamide in a mass ratio of 1: 3;

390 parts of a composition of N-octadecyl acrylamide and octadecyl vinyl ether in a mass ratio of 1: 2;

0.18 part of composition of lauroyl peroxide and tert-butyl peroxypivalate in the mass ratio of 1: 1;

3.2 parts of a composition of azobisisobutyronitrile and azobisisobutyric acid in a mass ratio of 1: 1;

5.6 parts of azodicyano valeric acid and azodiisoheptanonitrile composition in a mass ratio of 1: 1;

7.6 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester in a mass ratio of 1: 1;

7.2 parts of a composition of 1, 3-bis (4-aminophenoxy) propane and cyclobutane tetracarboxylic dianhydride in a mass ratio of 3: 1;

0.26 part of sodium methallyl sulfonate;

11.94 parts of super concentrated emulsifier;

6.0 parts of a composition of cetyl alcohol and stearyl methacrylate in a mass ratio of 3: 2;

1.2 parts of a composition of polyvinyl alcohol and hydroxypropyl cellulose in a mass ratio of 1: 1;

42 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1: 1;

8.3 parts of composition of ethanolamine and diethanolamine according to the mass ratio of 1: 2;

5.2 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 1: 1;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The preparation process of the high-temperature resistant amido alkyl super-concentrated emulsion polymer comprises the following steps:

1) directly adding 5.0 parts of water, 3.0 parts of cinnamamide and a composition of (4-vinylbenzene) sulfonamide in a mass ratio of 1:1, 3.5 parts of N-octadecyl acrylamide and a composition of octadecyl vinyl ether in a mass ratio of 1:1, 0.18 part of lauroyl peroxide and tert-butyl peroxypivalate in a mass ratio of 1:1 and 0.26 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 80 ℃ for 1.5 hours, preserving heat for 1 hour, and cooling to obtain the super-concentrated emulsifier.

2) Adding 17 parts of a composition of 2-acrylamide phenylboronic acid and 4-ethylene benzamide with the mass ratio of 1:3, 390 parts of a composition of N-octadecyl acrylamide and octadecyl vinyl ether with the mass ratio of 1:2, 7.6 parts of a composition of pyromellitic dianhydride hydroxyethyl dimethacrylate and bis (methacryloyloxyethyl) pyromellitic dianhydride ester with the mass ratio of 1:1, 42 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate with the mass ratio of 1:1 and 7.2 parts of a composition of 1, 3-bis (4-aminophenoxy) propane and cyclobutane tetracarboxylic dianhydride with the mass ratio of 3:1 into a three-neck flask provided with a stirring device and a condensation reflux device, adding 8.3 parts of a composition of ethanolamine and diethanolamine with the mass ratio of 1:2, adjusting the pH to 9-9.5, uniformly stirring, preparing a reaction monomer mixed solution;

3) adding 13 parts of deionized water, 11.94 parts of the super-concentrated emulsifier prepared in the step (1), 6.0 parts of a composition of cetyl alcohol and stearyl methacrylate in a mass ratio of 3:2 and 1.2 parts of a composition of polyvinyl alcohol 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, 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 2 minutes at the speed of 1100 r/min;

6) placing a centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 70 ℃ water bath at a constant temperature for 6 hours, dropwise adding the solution A for 5 hours, and dropwise adding the solution B for 1 hour, wherein the solution A comprises 50 parts of water and 3.2 parts of a composition of azodiisobutyronitrile and azodiisobutyronitrile in a mass ratio of 1:1, and the solution B comprises 50 parts of water and 5.6 parts of a composition of azodicyanopropionic acid and azodiisoheptonitrile in a mass ratio of 1: 1;

7) after the reaction is finished, preserving heat, curing for 1 hour, adding 5.2 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 1:1, and supplementing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

Example 6

A preparation method of a high-temperature resistant amide alkyl super-concentrated emulsion polymer mainly comprises the following components:

2.5 parts of cinnamamide;

octadecyl vinyl ether 2.9 parts;

26 parts of 2-acrylamide phenylboronic acid;

395 parts of N-octadecyl acrylamide;

0.13 part of tert-butyl peroxypivalate;

2.5 parts of dimethyl azodiisobutyrate;

3.3 parts of azodicyano valeric acid;

8.9 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester;

6.8 parts of 4, 4-diaminodiphenyl ether;

0.18 part of sodium methallyl sulfonate;

9.51 parts of super concentrated emulsifier;

7.0 parts of hexadecane;

1.4 parts of polyvinyl alcohol;

31 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 3: 2;

5.8 parts of ethanolamine;

8.1 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 1: 1;

the balance of water.

The total mass is 1000, and the solid content is 50%.

The preparation process of the high-temperature resistant amido alkyl super-concentrated emulsion polymer comprises the following steps:

1) directly adding 3.8 parts of water, 2.5 parts of cinnamamide, 2.9 parts of octadecyl vinyl ether, 0.13 part of tert-butyl peroxypivalate and 0.18 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 1.5 hours at 86 ℃, preserving heat for 1.5 hours, and cooling to obtain the super-concentrated emulsifier.

2) Adding 26 parts of 2-acrylamidophenylboronic acid, 395 parts of N-octadecyl acrylamide, 8.9 parts of bis (methacryloyloxyethyl) pyromellitic dianhydride ester, 31 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 3:2 and 6.8 parts of 4, 4-diaminodiphenyl ether into a three-neck flask provided with a stirring device and a condensation reflux device, adding 5.8 parts of ethanolamine to adjust the pH value to 9-9.5, and uniformly stirring to prepare a reaction monomer mixed solution;

3) adding 13 parts of deionized water, 9.51 parts of the super-concentrated emulsifier prepared in the step (1), 7.0 parts of hexadecane and 1.4 parts of polyvinyl alcohol 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 20 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 1100 r/min;

6) placing the centrifuged centrifugal test tube containing the ultra-concentrated emulsion in a 67 ℃ water bath at a 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 2.5 parts of dimethyl azodiisobutyrate, and the solution B comprises 50 parts of water and 3.3 parts of azodicyano valeric acid;

7) after the reaction is finished, preserving heat, curing for 1 hour, adding 8.1 parts of a composition of potassium hydroxide and sodium bicarbonate with the mass ratio of 1:1, and replenishing water until the mass of the total solution is 1000 parts, thus preparing the high-temperature resistant amidoalkyl super-concentrated emulsion polymer with the mass fraction of 50%.

The product was tested to obtain the following table.

As can be seen from the above table, the amidoalkyl super emulsion polymer of the present invention has many excellent properties, which are improved compared with the conventional polymer. The combination of example 5 shows that the invention has the advantages of excellent performance, strong water resistance, long service life, good low-temperature flexibility, higher tensile strength, no after tack, fast drying time and short secondary construction time. Meanwhile, 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.