Cationic waterproof agent dispersion and preparation method thereof

Abstract

The invention belongs to the technical field of fine chemical engineering, and discloses a cationic waterproof agent dispersion which comprises the following raw materials in parts by weight: 5-10 parts of hyperbranched polyethyleneimine, 10-50 parts of perfluoroalkyl carboxylic acid, 1-5 parts of hydrochloric acid, 5-50 parts of ethylene glycol butyl ether or propylene glycol butyl ether and 50-250 parts of deionized water. The preparation method comprises the following preparation steps: S1, adding hyperbranched polyethyleneimine and perfluoroalkyl carboxylic acid into ethylene glycol monobutyl ether or propylene glycol monobutyl ether, heating to 80-120 DEG C, and carrying out stirring reaction for 30 minutes to obtain a waterproof agent intermediate; s2, cooling the intermediate obtained in the step S1 to 30-40 DEG C, adding hydrochloric acid, and carrying out a neutralization reaction for 30 min; s3, deionized water is added, dispersion is conducted for 30 min under the stirring condition that the rotating speed is larger than 1000 r / min, and a target waterproof agent finished product is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a cationic waterproofing agent dispersion and a preparation method thereof. Background Art

[0002] In modern society, people have put forward more and more functional requirements for textiles. In daily life, people often encounter rainy days or other situations that require waterproofing, such as outdoor sports, construction industry, etc., so how to improve the waterproof performance of textiles is particularly important.

[0003] In the current printing and dyeing process, cationic polyacrylate emulsions containing perfluoroalkyl side chains are widely used as waterproofing agents for textiles. Generally, textiles themselves are negatively charged, so when this type of waterproofing agent is used, it combines with the fabric by means of the electrostatic attraction between the positive and negative charges, and is further fixed on the fabric surface by means of the cross-linking effect of the cross-linking agent. The perfluoroalkyl side chains with extremely low surface energy are enriched on the fabric surface, so that the finished fabric also exhibits extremely low surface energy, thereby achieving waterproof and even oil-proof properties.

[0004] The current cationic waterproofing agent emulsions are basically copolymers of fluorinated acrylate monomers and conventional acrylate monomers. Because fluorinated acrylates are difficult to emulsify, a large amount of emulsifiers need to be added during the synthesis process to form a stable emulsion. The current process generally uses a mixture of cationic emulsifiers and non-ionic emulsifiers. This type of waterproofing agent will produce a large amount of foam during use due to the large amount of emulsifiers used, which is very easy to form foam spots on the cloth surface, thereby affecting the quality of the finished cloth; at the same time, during the drying and film-forming process of the waterproofing agent, the small molecule emulsifier has extremely high mobility and is easy to be enriched on the film surface. The hydrophilic groups it carries will greatly reduce the application effect of the waterproofing agent. In addition, the easy crystallization of the perfluoroalkyl side chain often leads to a stiff feel of the fabric after waterproofing. In view of the above problems, the market urgently needs to improve the existing waterproofing agent system to overcome the existing defects. Summary of the invention

[0005] In view of the problems raised by the above background technology, the purpose of the present invention is to provide a cationic waterproofing agent dispersion and a preparation method thereof.

[0006] In order to achieve the above technical objectives, the technical solution adopted by the present invention is as follows:

[0007] A cationic waterproofing agent dispersion comprises the following raw materials in parts by weight: 5-10 parts of hyperbranched polyethyleneimine, 10-50 parts of perfluoroalkyl carboxylic acid, 1-5 parts of hydrochloric acid, 5-50 parts of ethylene glycol butyl ether or propylene glycol butyl ether, and 50-250 parts of deionized water;

[0008] A method for preparing a cationic waterproofing agent dispersion comprises the following steps:

[0009] S1. Add hyperbranched polyethyleneimine and perfluoroalkyl carboxylic acid to ethylene glycol butyl ether or propylene glycol butyl ether, raise the temperature to 80-120° C., and stir the reaction for 30 minutes to obtain a waterproofing agent intermediate;

[0010] S2, cooling the intermediate obtained in step S1 to 30-40°C, adding hydrochloric acid, and neutralizing for 30 minutes;

[0011] S3. Add deionized water and disperse for 30 minutes under stirring conditions at a speed greater than 1000 r / min to obtain the target waterproofing agent finished product.

[0012] Further defined, the hyperbranched polyethyleneimine is selected from one or any combination of molecular weights ranging from 10,000 to 30,000, and its molecular structure is as follows Figure 1 .

[0013] It is further defined that the perfluoroalkyl carboxylic acid is one or any combination of perfluoroheptanoic acid, perfluorooctanoic acid or perfluorononanoic acid.

[0014] It is further defined that the hydrochloric acid is industrial hydrochloric acid having a mass fraction concentration of 36%.

[0015] The beneficial effects of the present invention are as follows:

[0016] Compared with traditional fluorinated polyacrylate emulsion waterproofing agents, the waterproofing agent dispersion prepared by the present invention does not require the use of small molecule emulsifiers, and therefore has the characteristics of low foaming and excellent waterproofing performance; at the same time, the application of hyperbranched structural materials also makes the finished fabric have a softer feel. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The present invention can be further illustrated by the non-limiting examples given in the accompanying drawings;

[0018] Figure 1 The molecular structure diagram of the hyperbranched polyethyleneimine of the present invention is as follows:

[0019] Figure 2 The present invention is a schematic flow chart of a method for preparing a cationic waterproofing agent dispersion. DETAILED DESCRIPTION

[0020] In order to enable those skilled in the art to better understand the present invention, the technical solution of the present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0021] like Figure 1 , Figure 2As shown, a cationic waterproofing agent dispersion of the present invention comprises the following raw materials in parts by weight: 5 to 10 parts of hyperbranched polyethyleneimine, 10 to 50 parts of perfluoroalkyl carboxylic acid, 1 to 5 parts of hydrochloric acid, 5 to 50 parts of ethylene glycol butyl ether or propylene glycol butyl ether, and 50 to 250 parts of deionized water;

[0022] A method for preparing a cationic waterproofing agent dispersion comprises the following steps:

[0023] S1. Add hyperbranched polyethyleneimine and perfluoroalkyl carboxylic acid to ethylene glycol butyl ether or propylene glycol butyl ether, raise the temperature to 80-120° C., and stir the reaction for 30 minutes to obtain a waterproofing agent intermediate;

[0024] S2, cooling the intermediate obtained in step S1 to 30-40°C, adding hydrochloric acid, and neutralizing for 30 minutes;

[0025] S3. Add deionized water and disperse for 30 minutes under stirring conditions at a speed greater than 1000 r / min to obtain the target waterproofing agent finished product.

[0026] In this embodiment, hyperbranched polyethyleneimine is an important commercial hyperbranched polymer, which is a hyperbranched polymer consisting of amino groups and ~CH2~CH2~ intervals and contains primary, secondary and tertiary amines on the molecular chain. Hyperbranched polyethyleneimine is the polymer with the highest amino content known. The amino group can be easily neutralized by acid-base reaction to form various cationic materials. At the same time, its hyperbranched molecular structure makes it exhibit excellent softness.

[0027] The perfluoroalkyl carboxylic acid is subjected to a neutralization reaction with a hyperbranched polyethyleneimine to fix the perfluoroalkyl side chain to the molecular chain of the hyperbranched polyethyleneimine, and then the remaining amino groups of the hyperbranched polyethyleneimine are neutralized with hydrochloric acid to increase its hydrophilicity and cationicity, and finally the cationic waterproofing agent dispersion is prepared by stirring and dispersing in water under certain conditions;

[0028] Unlike conventional cationic waterproofing agent emulsions that require the addition of a large amount of cationic and nonionic emulsifiers during the preparation process, the cationic waterproofing agent dispersion prepared by the present invention does not use a small molecule emulsifier during the preparation process. It uses hydrochloric acid to neutralize the remaining amino groups on the hyperbranched polyethyleneimine to form ionizable ammonium chloride groups, which not only imparts cationicity but also ensures that it can be stably dispersed in water. Therefore, the cationic waterproofing agent dispersion prepared by the present invention basically eliminates the foam problem caused by the introduction of a large amount of emulsifiers during the use of conventional waterproofing agent emulsions, and also limits the negative impact of the accumulation of small molecule emulsifiers on the membrane surface on the waterproof effect to a certain extent. In addition, the hyperbranched structure destroys the regularity and symmetry of the molecular chain, thereby effectively preventing the occurrence of the perfluoroalkyl crystallization process, so that the fabric after waterproofing treatment has a relatively soft feel.

[0029] Specific recipe:

[0030] Embodiment 1:

[0031] Add 5 parts of hyperbranched polyethyleneimine with a molecular weight of 10,000 and 10 parts of perfluoroalkyl octanoic acid to 15 parts of ethylene glycol butyl ether, heat to 100°C and stir to react for 30 minutes to obtain a waterproofing agent intermediate, then cool to about 40°C, add 1 part of hydrochloric acid to the intermediate, neutralize for 30 minutes, and finally add 50 parts of deionized water, disperse for 30 minutes at a stirring condition of 1000r / min to obtain the target waterproofing agent finished product.

[0032] Embodiment 2:

[0033] Add 5 parts of hyperbranched polyethyleneimine with a molecular weight of 30,000 and 30 parts of perfluoroalkyl octanoic acid to 35 parts of ethylene glycol butyl ether, heat to 100°C and stir for reaction for 30 minutes to obtain a waterproofing agent intermediate, then cool to about 40°C, add 2 parts of hydrochloric acid to the intermediate, neutralize for 30 minutes, and finally add 120 parts of deionized water, disperse for 30 minutes at a stirring condition of 2000r / min to obtain the target waterproofing agent finished product.

[0034] Embodiment 3:

[0035] 5 parts of hyperbranched polyethyleneimine with a molecular weight of 10,000 and 20 parts of perfluoroalkylheptanoic acid are added to a mixed solvent of 15 parts of ethylene glycol butyl ether and 5 parts of propylene glycol butyl ether, the temperature is raised to 80°C and stirred for reaction for 30 minutes to obtain a waterproofing agent intermediate, then the temperature is lowered to about 40°C, 1.5 parts of hydrochloric acid are added to the intermediate, neutralization reaction is carried out for 30 minutes, and finally 100 parts of deionized water are added, and dispersion is carried out at a stirring condition of a speed of 2000r / min for 30 minutes to obtain the target waterproofing agent finished product.

[0036] Embodiment 4:

[0037] 5 parts of hyperbranched polyethyleneimine with a molecular weight of 10,000, 10 parts of perfluoroalkyl octanoic acid and 10 parts of perfluoroalkyl heptanoic acid are added to 25 parts of ethylene glycol butyl ether, the temperature is raised to 100°C and stirred for reaction for 30 minutes to obtain a waterproofing agent intermediate, then the temperature is lowered to about 40°C, 1.5 parts of hydrochloric acid are added to the intermediate, neutralization reaction is carried out for 30 minutes, and finally 80 parts of deionized water are added, and the mixture is dispersed at a stirring speed of 2000r / min for 30 minutes to obtain the target waterproofing agent finished product.

[0038] Embodiment 5:

[0039] 5 parts of hyperbranched polyethyleneimine with a molecular weight of 30,000 and 10 parts of perfluoroalkyl nonanoic acid are added to 15 parts of ethylene glycol butyl ether, the temperature is raised to 100°C and stirred for reaction for 30 minutes to obtain a waterproofing agent intermediate, then the temperature is lowered to about 40°C, 1 part of hydrochloric acid is added to the intermediate, neutralization reaction is carried out for 30 minutes, and finally 100 parts of deionized water are added, and the mixture is dispersed for 30 minutes under stirring conditions at a speed of 2000r / min to obtain the target waterproofing agent finished product.

[0040] Embodiment 6:

[0041] Add 5 parts of hyperbranched polyethyleneimine with a molecular weight of 30,000 and 30 parts of perfluoroalkyl octanoic acid into 35 parts of ethylene glycol butyl ether, heat to 100°C and stir for reaction for 30 minutes to obtain a waterproofing agent intermediate, then cool to about 40°C, add 2 parts of hydrochloric acid to the intermediate, neutralize for 30 minutes, and finally add 150 parts of deionized water, disperse for 30 minutes at a stirring speed of 2000r / min to obtain the target waterproofing agent finished product.

[0042] Embodiment 7:

[0043] Mix 5 parts of hyperbranched polyethyleneimine with a molecular weight of 10,000 and 5 parts of hyperbranched polyethyleneimine with a molecular weight of 30,000, add 30 parts of perfluoroalkyl octanoic acid, then add 30 parts of ethylene glycol butyl ether and 10 parts of propylene glycol butyl ether, heat to 100°C and stir to react for 30 minutes to obtain a waterproofing agent intermediate, then cool to about 40°C, add 2.5 parts of hydrochloric acid to the intermediate, neutralize for 30 minutes, finally add 200 parts of deionized water, disperse for 30 minutes at a stirring condition of 2000r / min to obtain the target waterproofing agent finished product.

[0044] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the technology may modify or change the above embodiments without violating the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical ideas disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A cationic waterproofing agent dispersion, characterized in that: The invention comprises the following raw materials in parts by weight: 5-10 parts of hyperbranched polyethyleneimine, 10-50 parts of perfluoroalkyl carboxylic acid, 1-5 parts of hydrochloric acid, 5-50 parts of ethylene glycol butyl ether or propylene glycol butyl ether and 50-250 parts of deionized water.

2. A cationic waterproofing agent dispersion according to claim 1, characterized in that: The hyperbranched polyethyleneimine has a molecular weight ranging from 10,000 to 30,000 or any combination thereof.

3. A cationic waterproofing agent dispersion according to claim 2, characterized in that: The perfluoroalkyl carboxylic acid is one or any combination of perfluoroheptanoic acid, perfluorooctanoic acid or perfluorononanoic acid.

4. A cationic water repellent dispersion according to claim 3, characterized in that: The hydrochloric acid is industrial hydrochloric acid with a mass fraction concentration of 36%.

5. A cationic waterproofing agent dispersion and a method for preparing the same, comprising the cationic waterproofing agent dispersion according to claim 1 to claim 4, characterized in that: The method comprises the following preparation steps: S1. Add hyperbranched polyethyleneimine and perfluoroalkyl carboxylic acid to ethylene glycol butyl ether or propylene glycol butyl ether, raise the temperature to 80-120° C., and stir the reaction for 30 minutes to obtain a waterproofing agent intermediate; S2, cooling the intermediate obtained in step S1 to 30-40°C, adding hydrochloric acid, and neutralizing for 30 minutes; S3. Add deionized water and disperse for 30 minutes under stirring conditions at a speed greater than 1000 r / min to obtain the target waterproofing agent finished product.

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