CN112029027A - Graphene composite cationic emulsion and preparation method thereof - Google Patents
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Abstract
The invention discloses a graphene composite cationic emulsion, which comprises hard monomers, soft monomers, cationic monomers, graphene powder, cationic emulsifiers, nonionic emulsifiers, anionic emulsifiers, initiators and water as raw materials. The invention also discloses a preparation method of the graphene composite cationic emulsion, which comprises the steps of firstly carrying out surface functional modification on graphene through an anionic emulsifier to enable the graphene to carry negative charges, then introducing a cationic functional monomer to synthesize the cationic emulsion carrying the positive charges by adopting an emulsion polymerization process, finally dispersing the functionalized graphene in the cationic emulsion, and obtaining the stable graphene composite cationic emulsion under the action of electrostatic attraction. The method is simple in process, environment-friendly and suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of novel graphene materials and textiles, and particularly relates to graphene composite cationic emulsion and a preparation method thereof.
Background
With the development of textile technology and the improvement of living standard of people, the wearability of traditional fabrics is difficult to meet the requirements of high-end markets, the multifunctional properties (antistatic property, bacteriostasis, water repellency, oil repellency, flame retardance, ultraviolet resistance and the like) of the fabrics become new requirements of people for clothing, and especially the development of fabric products with the functions of antistatic property, bacteriostasis and the like becomes a research hotspot in the technical field of textile.
Graphene is a polymer made of carbon atoms in sp2The hybridization track forms a hexagonal ring-shaped honeycomb crystalline ultrathin material, and the unique two-dimensional sheet structure of the ultrathin material can cut and destroy bacterial cell membranes and adsorb phospholipid molecules on the cell membranes, so that bacteria are inactivated to achieve the bacteriostatic effect. The graphene also has excellent conductivity, and the special energy band structure of the graphene enables the graphene to have extremely high electron transfer rate which reaches 15000cm2V · s. Therefore, the graphene has significance in the technical field of textilesThe graphene can be attached to the surface of the fabric fiber through a fabric finishing process, and the fabric is endowed with a multifunctional characteristic. Chinese patents CN201810383225.8 and CN201510540291.8 both disclose a method for obtaining graphene composite fabric by using graphene oxide aqueous solution as finishing agent, and immersing, drying and reducing the fabric, but because the graphene and the fabric lack chemical bond, the bonding strength of the graphene and the fabric is general, and the use of reducing agent increases the preparation process and has harm to human body and environment. Chinese patent CN201810138905.3 discloses a preparation method for dispersing graphene in traditional acrylic emulsion to obtain a graphene multifunctional fabric finishing agent, the method is simple in process, but graphene in the finishing emulsion is easy to agglomerate and stack due to the fact that the graphene is not subjected to surface modification, and stability and finishing performance of the graphene multifunctional fabric finishing agent are poor.
Therefore, the problem to be solved by the technical personnel in the field is how to provide the graphene composite cationic emulsion with good finishing performance and the preparation method thereof.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a graphene composite cationic emulsion. The graphene composite cationic emulsion can be used for functionally finishing fabrics, so that the fabrics have the dual functions of static resistance and bacteria resistance, and the positive charges contained in the graphene composite cationic emulsion can generate an ionic bond effect with negative charges on the surfaces of fabric fibers, so that the graphene composite cationic emulsion has good binding fastness to the fabrics.
In order to achieve the purpose, the invention adopts the following technical scheme:
the graphene composite cationic emulsion is prepared from the following raw material components in parts by mass:
further, the hard monomer is selected from one or more of styrene, methyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate;
the soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, ethoxy ethyl acrylate and isotridecyl acrylate;
the cationic monomer is selected from one or more of methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide, methacryloyloxyethyl dimethyl tetradecyl ammonium bromide, methacryloyloxyethyl dimethyl hexadecyl ammonium bromide and diallyl ethyl benzyl ammonium chloride;
the initiator is selected from one of azodiisopropyl imidazoline hydrochloride, azodiisopropyl amidine hydrochloride, azodicarboxyethyl-2-isobutyl amidine hydrate and azodiisopropyl imidazoline.
The technical effect of adopting the technical scheme is as follows: the hard monomer and the soft monomer are common monomers in the technical field of emulsion polymerization, and the glass transition temperature of the graphene composite cationic emulsion polymer can be regulated and controlled by changing the proportion of the hard monomer and the soft monomer in the components through tests, so that the softness of the emulsion polymer and the physical properties such as the binding fastness to fabrics are effectively improved; the cationic monomer is a quaternary ammonium salt cationic functional monomer containing olefin double bonds, can participate in polymerization and introduces positive charges which are difficult to desorb on a polymer chain segment, and is beneficial to improving the stability of the graphene composite emulsion and the binding fastness of the graphene composite emulsion to fabrics; the initiators are all water-soluble azo initiators, the radicals generated by decomposition have positive charges, the electric property of the radicals is the same as that of emulsion particles, and the polymerization of the radicals to the surfaces of the emulsion particles is beneficial to improving the stability of the graphene composite cationic emulsion.
Further, the anionic emulsifier is selected from one of sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and sodium hexadecyl sulfate;
the cationic emulsifier is selected from one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride;
the non-ionic emulsifier is one selected from alkylphenol ethoxylates, propylene oxide-ethylene oxide copolyether, sorbitan monofatty acid ester and polyoxyethylene sorbitan monofatty acid ester.
The technical effect of adopting the technical scheme is as follows: by adopting the anionic emulsifier to functionally modify the surface of the graphene, the dispersibility of the graphene is improved, and the graphene and the cationic emulsion generate electrostatic adsorption, so that the problem that the graphene is easy to agglomerate is solved, and the stable graphene composite cationic emulsion is obtained. By adopting the cationic emulsifier and the nonionic emulsifier and combining a cationic emulsion polymerization process, the cationic monomer is introduced, the cationic monomer and the graphene can play a synergistic antibacterial effect, and meanwhile, the rich amino group can generate an ionic bond effect with negative charges carried on the surface of fabric fibers, so that the fabric bonding fastness and the washing fastness of the graphene can be improved when the cationic emulsifier and the nonionic emulsifier are used for fabric finishing.
The invention also aims to provide a preparation method of the graphene composite cationic emulsion for fabric finishing. According to the invention, firstly, graphene is functionally modified to enable the surface of the graphene to carry negative charges, then, an emulsion polymerization process is adopted to synthesize a cationic emulsion with the surface carrying the positive charges, and finally, the modified graphene is dispersed in the cationic emulsion to obtain a stable graphene composite cationic emulsion under the action of electrostatic attraction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the graphene composite cationic emulsion is characterized by comprising the following steps:
s1, sequentially adding graphene powder and an anionic emulsifier into a proper amount of water, and uniformly dispersing by ultrasonic, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-6 h to obtain a graphene dispersion liquid;
s2, sequentially putting a hard monomer, a soft monomer, a cationic emulsifier, a nonionic emulsifier and a proper amount of water into a reaction kettle, introducing protective gas, adding an initiator aqueous solution prepared from an initiator and water after the temperature is raised to 70-85 ℃, polymerizing, reducing the system temperature to below 40 ℃ after reacting for 3-6 h at a constant temperature, and controlling the pH of the emulsion to be 5-6 by using a pH regulator to obtain a cationic emulsion;
s3, ultrasonically dispersing the graphene dispersion liquid obtained in the step S1 and the cationic emulsion obtained in the step S2 uniformly, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-3 h, so that the graphene composite cationic emulsion is obtained.
Further, in the step S1, the mass ratio of the graphene powder, the anionic emulsifier and the water is 0.1-1: 0.3-2: 15-30.
Further, in step S2, the mass ratio of the hard monomer, the soft monomer, the cationic emulsifier, the nonionic emulsifier and the water is 10-30: 10-25: 0.5-4: 0.5-1.5: 35-65.
Further, in step S2, the protective gas is selected from one of nitrogen, helium and argon.
The technical effect of adopting the technical scheme is as follows: because oxygen is polymerization inhibitor of emulsion polymerization, protective gas is introduced, oxygen contained in the system can be effectively removed, thereby reducing the dosage of the initiator and improving the process stability of cationic emulsion polymerization.
Further, in step S2, the mass concentration of the initiator aqueous solution is 10-30 mg/mL.
The technical effect of adopting the technical scheme is as follows: the problems of over-high reaction rate and poor system stability of a polymerization system caused by over-high local initiator concentration can be effectively avoided by adopting an initiator aqueous solution adding mode.
Further, in step S2, the pH adjusting agent is selected from one of glacial acetic acid, diluted hydrochloric acid and diluted sulfuric acid.
The technical effect of adopting the technical scheme is as follows: the pH regulator can effectively control the pH value of the cationic emulsion, the preferable pH value range of the emulsion is 5-6, and the stability of the cationic emulsion can be influenced by overhigh or overlow pH value.
Further, in step S3, the mass ratio of the graphene dispersion to the cationic emulsion is: 0.2-1: 1.
The invention further provides application of the graphene composite cationic emulsion prepared by the preparation method of the graphene composite cationic emulsion in fabric finishing.
According to the technical scheme, compared with the prior art, the invention discloses the graphene composite cationic emulsion which has the following technical effects:
(1) according to the invention, the graphene surface is functionally modified, so that the dispersibility of the graphene is improved, and the graphene and the cationic emulsion generate electrostatic adsorption, the problem that the graphene is easy to agglomerate is solved, and the stable graphene composite cationic emulsion is obtained.
(2) The graphene has high conductivity and antibacterial activity, and the graphene composite cationic emulsion provided by the invention can be used for functionally finishing the fabric, so that the fabric can have good antistatic and antibacterial properties.
(3) According to the invention, the cationic monomer is introduced through a cationic emulsion polymerization process, so that the cationic monomer and graphene can play a synergistic antibacterial role, and meanwhile, the rich amino group can generate an ionic bond effect with negative charges carried on the surface of fabric fibers, so that the fabric binding fastness and the washing fastness of the graphene can be improved when the fabric is used for fabric finishing.
(4) According to the preparation method of the graphene composite cationic emulsion, the emulsion polymerization process is adopted, the graphene does not need to be reduced, the use of a toxic reducing agent for a human body is avoided, and the method is simple in process, green and environment-friendly and suitable for industrial mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing the test effect of the graphene composite cationic emulsion obtained in example 1 of the present invention after standing for 30 days.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The starting materials mentioned in the examples are commercially available, and for example, styrene, methyl methacrylate, methacryloyloxyethyldimethylbenzylammonium chloride, methacryloyloxyethyldimethyldodecylammonium bromide and the like are the reagents conventionally used by those skilled in the art. No requirement is made on the brand source, and the description is omitted here.
The embodiment of the invention provides a graphene composite cationic emulsion which is prepared from the following raw material components in parts by mass:
in order to further optimize the technical scheme, the hard monomer is selected from one or more of styrene, methyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate;
the soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, ethoxy ethyl acrylate and isotridecyl acrylate;
the cationic monomer is selected from one or more of methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide, methacryloyloxyethyl dimethyl tetradecyl ammonium bromide, methacryloyloxyethyl dimethyl hexadecyl ammonium bromide and diallyl ethyl benzyl ammonium chloride;
the initiator is one selected from azodiisopropyl imidazoline hydrochloride, azodiisopropyl amidine hydrochloride, azodicarboxyethyl-2-isobutyl amidine hydrate and azodiisopropyl imidazoline.
In order to further optimize the technical scheme, the anionic emulsifier is selected from one of sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and sodium hexadecyl sulfate;
the cationic emulsifier is selected from one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride;
the nonionic emulsifier is one selected from alkylphenol ethoxylate, propylene oxide-ethylene oxide copolyether, sorbitan monofatty acid ester and polyoxyethylene sorbitan monofatty acid ester.
The embodiment of the invention also provides a preparation method of the graphene composite cationic emulsion, which is characterized by comprising the following steps:
s1, sequentially adding graphene powder and an anionic emulsifier into a proper amount of water, and uniformly dispersing by ultrasonic, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-6 h to obtain a graphene dispersion liquid;
s2, sequentially putting a hard monomer, a soft monomer, a cationic emulsifier, a nonionic emulsifier and a proper amount of water into a reaction kettle, introducing protective gas, adding an initiator aqueous solution prepared from an initiator and water after the temperature is raised to 70-85 ℃, polymerizing, reducing the system temperature to below 40 ℃ after reacting for 3-6 h at a constant temperature, and controlling the pH of the emulsion to be 5-6 by using a pH regulator to obtain a cationic emulsion;
s3, ultrasonically dispersing the graphene dispersion liquid obtained in the step S1 and the cationic emulsion obtained in the step S2 uniformly, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-3 h, so that the graphene composite cationic emulsion is obtained.
In order to further optimize the technical scheme, in step S1, the mass ratio of the graphene powder, the anionic emulsifier and the water is 0.1-1: 0.3-2: 15-30.
In order to further optimize the technical scheme, in step S2, the mass ratio of the hard monomer, the soft monomer, the cationic emulsifier, the nonionic emulsifier and the water is 10-30: 10-25: 0.5-4: 0.5-1.5: 35-65.
In order to further optimize the above technical solution, in step S2, the protective gas is selected from one of nitrogen, helium and argon.
In order to further optimize the technical scheme, in step S2, the mass concentration of the initiator aqueous solution is 10-30 mg/mL.
In order to further optimize the technical scheme, the pH regulator is selected from one of glacial acetic acid, diluted hydrochloric acid and diluted sulfuric acid.
In order to further optimize the above technical solution, in step S3, the mass ratio of the graphene dispersion liquid to the cationic emulsion is: 0.2-1: 1.
Example 1
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 0.3g of graphene powder, 0.9g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 1.5 hours under the ultrasonic condition of 400W to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 50g of styrene, 48g of butyl acrylate, 2g of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 2g of octadecyl trimethyl ammonium chloride, 2g of propylene oxide-ethylene oxide copolyether and 126g of deionized water into a three-mouth flask, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of 15mg/mL of azodiisopropyl imidazoline hydrochloride aqueous solution into the flask when the temperature is raised to 82 ℃, reacting for 4 hours at constant temperature, reducing the system temperature to be below 40 ℃, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (4) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 1h under the 400W ultrasonic condition to obtain the graphene composite cationic emulsion.
Example 2
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 0.9g of graphene powder, 2g of sodium dodecyl benzene sulfonate and 50g of deionized water into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 50g of styrene, 48g of butyl acrylate, 2g of methacryloyloxyethyl dimethyl dodecyl ammonium bromide, 2g of hexadecyl trimethyl ammonium chloride, 2g of alkylphenol ethoxylates and 126g of deionized water into a three-neck flask, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of 15mg/mL of azodiisopropyl amidine hydrochloride aqueous solution into the flask when the temperature is raised to 82 ℃, reducing the system temperature to be below 40 ℃ after reacting for 4 hours at constant temperature, adjusting the pH value of the emulsion to be 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (4) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 1.5 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 3
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 4g of sodium hexadecylsulfonate and 50g of deionized water into a beaker, and dispersing for 3 hours under the ultrasonic condition of 500W to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 50g of styrene, 47g of butyl acrylate, 3g of methacryloyloxyethyl dimethyltetradecyl ammonium bromide, 2g of hexadecyltrimethyl ammonium bromide, 2g of sorbitan monofatty acid ester and 126g of deionized water into a three-neck flask, adopting nitrogen protection, starting a heating and stirring device, adding 15mg/mL of azodicarboxyethyl-2-isobutylamidine hydrate aqueous solution into the flask for 20mL when the temperature is raised to 82 ℃, reducing the system temperature to be below 40 ℃ after reacting for 4 hours at constant temperature, adjusting the pH value of the emulsion to be 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 4
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 3g of graphene powder, 6g of sodium hexadecyl sulfate and 50g of deionized water into a beaker, and dispersing for 6 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Adding 49g of styrene, 46g of butyl acrylate, 5g of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide, 2g of dodecyl trimethyl ammonium bromide, 2g of polyoxyethylene sorbitan monofatty acid ester and 126g of deionized water into a three-mouth flask in sequence, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of azodiisopropyl imidazoline aqueous solution of 15mg/mL into the flask when the temperature is raised to 82 ℃, reducing the system temperature to be below 40 ℃ after 5 hours of constant temperature reaction, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 3 hours under the 500W ultrasonic condition to obtain the graphene composite cationic emulsion.
Example 5
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 48g of methyl methacrylate, 49g of butyl acrylate, 3g of diallyl ethylbenzyl ammonium chloride, 2g of octadecyl trimethyl ammonium chloride, 2g of propylene oxide-ethylene oxide copolyether and 126g of deionized water into a three-mouth flask, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of 15mg/mL of azodiisopropyl imidazoline hydrochloride aqueous solution into the flask when the temperature is raised to 82 ℃, reducing the system temperature to be below 40 ℃ after constant temperature reaction for 4 hours, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 6
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 48g of methyl methacrylate, 48g of butyl acrylate, 4g of methacryloyloxyethyl dimethyl dodecyl ammonium bromide, 2g of octadecyl trimethyl ammonium chloride, 2g of propylene oxide-ethylene oxide copolyether and 126g of deionized water into a three-mouth flask, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of azodiisopropylamidine hydrochloride aqueous solution of 15mg/mL into the flask when the temperature is increased to 80 ℃, reacting at constant temperature for 4 hours, reducing the system temperature to be below 40 ℃, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 7
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 20g of styrene, 29g of methyl methacrylate, 47g of butyl acrylate, 4g of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 2g of hexadecyl trimethyl ammonium chloride, 2g of propylene oxide-ethylene oxide copolyether and 126g of deionized water into a three-mouth flask, starting a heating and stirring device under the protection of nitrogen, adding 20mL of azodicarboxyethyl-2-isobutyl amidine hydrate aqueous solution into the flask when the temperature is increased to 80 ℃, reducing the system temperature to be below 40 ℃ after reacting for 4 hours at constant temperature, adjusting the pH value of the emulsion to be 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 8
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 20g of styrene, 30g of methyl methacrylate, 47g of butyl acrylate, 3g of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 3g of hexadecyl trimethyl ammonium chloride, 2g of alkylphenol polyoxyethylene and 125g of deionized water into a three-mouth flask, starting a heating and stirring device under the protection of nitrogen, adding 20mL of 15mg/mL of azodiisopropyl imidazoline hydrochloride aqueous solution into the flask when the temperature is increased to 80 ℃, reacting at constant temperature for 4 hours, reducing the system temperature to be below 40 ℃, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Example 9
The embodiment provides a preparation method of a graphene composite cationic emulsion, which specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Adding 49g of methyl methacrylate, 37g of butyl acrylate, 10g of isooctyl acrylate, 4g of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 2g of hexadecyl trimethyl ammonium chloride, 2g of polyoxyethylene sorbitan monofatty acid ester and 126g of deionized water into a three-mouth flask in sequence, adopting nitrogen protection, starting a heating and stirring device, adding 25mg/mL of azodiisopropyl imidazoline hydrochloride aqueous solution into the flask for 20mL when the temperature is increased to 75 ℃, reducing the system temperature to be below 40 ℃ after 5 hours of constant temperature reaction, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Comparative example 1
The comparison example provides a preparation method of a graphene fabric finishing agent, and the difference from example 5 is that the prepared finishing agent is not compounded with a polymer emulsion, and specifically comprises the following steps: 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water are sequentially added into a beaker, and dispersed for 4 hours under the ultrasonic condition of 600W to prepare the uniform graphene fabric finishing agent.
Comparative example 2
The comparison example provides a preparation method of a graphene fabric finishing agent, which is different from example 5 in that a graphene dispersion liquid is compounded with a traditional anionic emulsion, and other preparation parameters are consistent, and the preparation method specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder, 3g of sodium hexadecylbenzene sulfonate and 50g of deionized water into a beaker, and dispersing for 4 hours under 600W ultrasonic condition to prepare uniform graphene dispersion liquid;
s2 preparation of graphene fabric finishing agent
And (4) adding the graphene dispersion liquid prepared in the step S1 and 300g of the traditional acrylic acid anion emulsion into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to prepare the graphene fabric finishing agent.
Comparative example 3
The comparative example provides a preparation method of a graphene composite cationic emulsion, which is different from the preparation method of example 5 in that an anionic emulsifier is not added in the preparation of a graphene dispersion liquid, and other preparation parameters are consistent. The method specifically comprises the following steps:
s1 preparation of graphene dispersion liquid
Sequentially adding 1.5g of graphene powder and 53g of deionized water into a beaker, and dispersing for 4 hours under the ultrasonic condition of 600W to prepare uniform graphene dispersion liquid;
s2 Synthesis of cationic emulsion
Sequentially adding 48g of methyl methacrylate, 49g of butyl acrylate, 3g of diallyl ethylbenzyl ammonium chloride, 2g of octadecyl trimethyl ammonium chloride, 2g of propylene oxide-ethylene oxide copolyether and 126g of deionized water into a three-mouth flask, adopting nitrogen protection, starting a heating and stirring device, adding 20mL of 15mg/mL of azodiisopropyl imidazoline hydrochloride aqueous solution into the flask when the temperature is raised to 82 ℃, reducing the system temperature to be below 40 ℃ after constant temperature reaction for 4 hours, adjusting the pH value of the emulsion to 5-6 by using dilute hydrochloric acid, and discharging to obtain the required cationic emulsion;
s3 preparation of graphene composite cationic emulsion
And (3) adding the graphene dispersion liquid in the step S1 and the cationic emulsion in the step S2 into a beaker, and dispersing for 2 hours under the ultrasonic condition of 500W to obtain the graphene composite cationic emulsion.
Performance testing
(1) Graphene composite cationic emulsion stability test
The materials provided in examples 1-9 and comparative examples 1-3 were tested, and the Zeta potential of the emulsion was measured using a Zeta potential analyzer (the average value was taken after three times of tests); standing the emulsion for 30 days to observe whether the emulsion is settled or not, and testing the standing stability of the emulsion; adding 0.5% calcium chloride aqueous solution into the emulsion (the mass ratio of the emulsion to the calcium chloride aqueous solution is 4: 1), standing for 1 day, and testing the calcium ion stability of the emulsion. The test results are shown in table 1:
TABLE 1
| Group of | [ Zeta ] potential/mV | Stability of standing | Stability of calcium ion |
| Example 1 | 67.3 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 2 | 65.6 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 3 | 64.2 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 4 | 61.3 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 5 | 63.8 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 6 | 66.1 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 7 | 65.4 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 8 | 64.2 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Example 9 | 65.1 | Without sedimentation | Without emulsion breaking, layering and small particle precipitation |
| Comparative example 1 | 25.2 | Sedimentation | Small particles are separated out |
| Comparative example 2 | 30.3 | Sedimentation | Small particles are separated out |
| Comparative example 3 | 33.1 | Sedimentation | Small particles are separated out |
As can be seen from the attached figure 1, the graphene composite cationic emulsion prepared in example 1 still has no sedimentation after standing for 30 days, and has no demulsification, delamination and small particle precipitation. As can be seen from Table 1, the graphene composite cationic emulsions prepared in the embodiments 1-9 of the invention all have excellent stability. The graphene fabric finishing agent prepared in the comparative examples 1-3 has general stability, because the graphene fabric finishing agent in the comparative example 1 is not compositely modified with the polymer emulsion; in the comparative example 2, the graphene and the traditional anionic emulsion are simply physically blended and have no ionic bond; in comparative example 3, no anionic emulsifier was added, and no ionic bond was formed between the graphene and the cationic emulsion.
(2) Fabric finishing Performance test
Selecting terylene as a test fabric, adopting a two-dipping two-drying finishing process to respectively dip the fabric into the graphene composite cationic emulsion provided in the examples 1-9 and the graphene fabric finishing agent provided in the comparative examples 1-3 at a bath ratio of 1: 50, and drying at 50 ℃ after dipping for 1 hour to obtain the functionalized finishing fabric.
The antistatic performance of the fabric was tested according to GB/T12703.4-2010, the test results are shown in Table 2:
TABLE 2
As can be seen from table 2, the fabric finished in embodiments 1 to 9 of the present invention has good antistatic performance, and after 50 times of washing, the fabric still has good antistatic performance, which indicates that the graphene composite cationic emulsion provided by the present invention can significantly improve the antistatic performance of the fabric when used for fabric finishing, and has excellent washing fastness.
The fabrics finished by the comparative examples 1-3 also have certain antistatic performance, but after 50 times of washing, the antistatic performance is obviously reduced, which shows that the graphene fabric finishing agent provided by the comparative examples has poor dispersibility of graphene, and poor binding fastness and washing fastness to fabrics due to no composite modification of graphene or lack of bonding effect between the graphene and emulsion.
The antibacterial performance of the fabric is tested according to GB/T20944.3-2008, and the test result is shown in Table 3:
TABLE 3
As can be seen from table 3, the fabric finished in embodiments 1 to 9 of the present invention has excellent antibacterial performance, and after 50 times of washing, the fabric still has a good antibacterial effect, which indicates that the graphene composite cationic emulsion provided by the present invention can improve antibacterial performance and has washability when used for fabric finishing.
The fabrics finished by the comparative examples 1-3 also have certain antibacterial performance, but after 50 times of washing, the antibacterial performance is obviously reduced, which shows that the graphene fabric finishing agent provided by the comparative examples has poor graphene dispersibility, poor fabric binding fastness and poor fabric washing fastness due to the fact that graphene is not subjected to composite modification or the graphene and emulsion are lack of bonding effect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The graphene composite cationic emulsion is characterized by comprising the following raw materials in percentage by mass:
2. the graphene composite cationic emulsion according to claim 1, wherein the hard monomer is one or more selected from styrene, methyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate;
the soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, ethoxy ethyl acrylate and isotridecyl acrylate;
the cationic monomer is selected from one or more of methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide, methacryloyloxyethyl dimethyl tetradecyl ammonium bromide, methacryloyloxyethyl dimethyl hexadecyl ammonium bromide and diallyl ethyl benzyl ammonium chloride;
the initiator is selected from one of azodiisopropyl imidazoline hydrochloride, azodiisopropyl amidine hydrochloride, azodicarboxyethyl-2-isobutyl amidine hydrate and azodiisopropyl imidazoline.
3. The graphene composite cationic emulsion according to claim 1, wherein the anionic emulsifier is selected from one of sodium hexadecylbenzene sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and sodium hexadecyl sulfate;
the cationic emulsifier is selected from one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride;
the non-ionic emulsifier is one selected from alkylphenol ethoxylates, propylene oxide-ethylene oxide copolyether, sorbitan monofatty acid ester and polyoxyethylene sorbitan monofatty acid ester.
4. The preparation method of the graphene composite cationic emulsion according to any one of claims 1 to 3, characterized by comprising the following steps:
s1, sequentially adding graphene powder and an anionic emulsifier into water, and uniformly dispersing by using ultrasonic, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-6 h to obtain a graphene dispersion liquid;
s2, sequentially putting a hard monomer, a soft monomer, a cationic emulsifier, a nonionic emulsifier and water into a reaction kettle, introducing protective gas, adding an initiator aqueous solution prepared from an initiator and water after the temperature is raised to 70-85 ℃, polymerizing, reducing the system temperature to below 40 ℃ after reacting at a constant temperature for 3-6 hours, and controlling the pH of the emulsion to be 5-6 by using a pH regulator to obtain a cationic emulsion;
s3, ultrasonically dispersing the graphene dispersion liquid obtained in the step S1 and the cationic emulsion obtained in the step S2 uniformly, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 0.5-3 h, so that the graphene composite cationic emulsion is obtained.
5. The method for preparing the graphene composite cationic emulsion according to claim 4, wherein in step S1, the mass ratio of the graphene powder, the anionic emulsifier and the water is 0.1-1: 0.3-2: 15-30.
6. The method for preparing the graphene composite cationic emulsion according to claim 4, wherein in step S2, the mass ratio of the hard monomer, the soft monomer, the cationic emulsifier, the nonionic emulsifier and the water is 10-30: 10-25: 0.5-4: 0.5-1.5: 35-65.
7. The method for preparing the graphene composite cationic emulsion according to claim 4, wherein in step S2, the protective gas is one selected from nitrogen, helium and argon.
8. The method for preparing the graphene composite cationic emulsion according to claim 4, wherein in step S2, the mass concentration of the initiator aqueous solution is 10-30 mg/mL.
9. The method for preparing the graphene composite cationic emulsion according to claim 4, wherein in step S2, the pH regulator is selected from one of glacial acetic acid, diluted hydrochloric acid and diluted sulfuric acid.
10. The application of the graphene composite cationic emulsion prepared by the method according to any one of claims 4 to 9 in fabric finishing.
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