CN113717307B - Polymer microsphere and preparation method and application thereof - Google Patents
Polymer microsphere and preparation method and application thereof Download PDFInfo
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- CN113717307B CN113717307B CN202111130289.5A CN202111130289A CN113717307B CN 113717307 B CN113717307 B CN 113717307B CN 202111130289 A CN202111130289 A CN 202111130289A CN 113717307 B CN113717307 B CN 113717307B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/34—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using natural dyestuffs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/605—Natural or regenerated cellulose dyeing with polymeric dyes; building polymeric dyes on fibre
- D06P3/6058—Natural or regenerated cellulose dyeing with polymeric dyes; building polymeric dyes on fibre by using dyes with polymerisable groups, e.g. dye ---CH=CH2
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Abstract
The invention relates to the technical field of polymer microspheres, and discloses a polymer microsphere, a preparation method and application thereof. The method comprises the following steps: (1) Mixing silicon-containing methylamine, chloropropene and absolute ethyl alcohol under stirring, heating to react under nitrogen atmosphere, and performing rotary evaporation, cooling, washing, recrystallization, vacuum filtration and vacuum drying to obtain silicon-containing cationic monomers; (2) Adding hydrophilic white carbon black into an ethanol aqueous solution, stirring and dispersing, adding a silane coupling agent in a stirring state, heating for condensation and reflux, cooling to room temperature, stopping stirring, washing, and drying to obtain modified white carbon black; (3) Styrene, N-t-butyl acrylamide, silicon cationic monomer, modified white carbon black, cross-linking agent and 2,2' -azo (2-methylpropionamidine) dihydrochloride are mixed, added with water and then reacted. The polymer microsphere prepared by the method can be combined with gardenia yellow dye, so that the ageing resistance of the dye is greatly improved, and a series of indexes after dyeing are also improved.
Description
Technical Field
The invention relates to the technical field of polymer microspheres, in particular to a polymer microsphere, a preparation method and application thereof.
Background
The natural dye source is automatic plants or minerals, has good environmental compatibility and quick degradation, has antibacterial performance, and is one of main colorants in the field of ecological textiles. The gardenia Huang Zuose is natural and has high saturation, and is one of yellow-brown natural dyes which are widely applied. The long chain structure of the gardenia yellow dye contains a large number of conjugated double bonds, so that the property of the gardenia yellow in an aqueous solution is unstable. When the gardenia yellow dye is subjected to illumination and oxygen, hydrolysis and oxidation are easy to occur, so that the structure is damaged, the fading reaction of the dye is caused, the gardenia yellow dye has the defect of poor light fastness and water fastness, and the application of the gardenia yellow dye in the aspect of functional textiles is restricted.
The polymer microsphere is a polymer aggregate with a spherical shape, has the advantages of large specific surface area, good monodispersity and various forms, and can be used for dyeing fibers, inkjet printing textile substrates and the like when being combined with dyes. There is no report on polymer microspheres suitable for adsorbing gardenia yellow dye.
Disclosure of Invention
The invention aims to solve the problem that the prior art does not have polymer microspheres suitable for adsorbing gardenia yellow dye, and provides a polymer microsphere, a preparation method and application thereof.
In order to achieve the above object, the present invention provides a method for preparing polymer microspheres, comprising the steps of:
(1) Stirring and mixing silicon-containing methylamine, chloropropene and absolute ethyl alcohol, heating to 40-55 ℃ under nitrogen atmosphere for reaction for 24-30h, performing reduced pressure rotary evaporation to remove small molecular low-boiling substances to obtain yellow transparent liquid, cooling to obtain white solid, and sequentially washing, recrystallizing, performing reduced pressure suction filtration and vacuum drying on the white solid to obtain silicon-type cationic monomer;
(2) Adding hydrophilic white carbon black into an ethanol water solution, wherein the weight ratio of the hydrophilic white carbon black to the ethanol water solution is 1: (20-50), stirring and dispersing, then adding a silane coupling agent in a stirring state, heating to 100-120 ℃ for condensation and reflux, wherein the time of the condensation and reflux is 2.5-4h, cooling to room temperature after the condensation and reflux is finished, stopping stirring, washing by using toluene, and drying to obtain the modified white carbon black;
(3) Mixing styrene, N-tertiary butyl acrylamide, the silicon cationic monomer obtained in the step (1), the modified white carbon black obtained in the step (2), a cross-linking agent and 2,2' -azo (2-methylpropionamidine) dihydrochloride to obtain a mixture, adding water to obtain slurry, wherein the slurry contains 8-24 weight percent of the mixture, and then reacting for 2.5-8 hours at 80-95 ℃;
Wherein in step (1), the molar ratio of the silicon-containing methylamine to the chloropropene is 1: (2.7-3.3); the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the silicon-containing methylamine and the weight of the chloropropene is (1.05-1.1): 1, a step of;
in the step (2), the weight ratio of the silane coupling agent to the hydrophilic white carbon black is (0.05-0.2): 1;
in the step (3), the cross-linking agent is at least one of dimethyl diallyl ammonium chloride, N-methylene bisacrylamide and N-methylolacrylamide;
the weight ratio of the N-tertiary butyl acrylamide, the silicon cationic monomer, the modified white carbon black and the styrene is (0.15-0.35): (0.02-0.08): (0.005-0.03): 1, a step of;
the ratio of the weight of the cross-linking agent to the sum of the weights of the styrene, the N-tertiary butyl acrylamide, the silicon cation monomer and the modified white carbon black is (0.002-0.01): 1;
the ratio of the weight of the 2,2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of the styrene, the N-t-butyl acrylamide, the silicon type cationic monomer and the modified white carbon black is (0.004-0.02): 1.
preferably, in step (1), the silicon-containing methylamine is at least one of N- (trimethylsilyl) dimethylamine, N- (trimethylsilyl) acetamide, and N, N-diethyltrimethylsilyl amine.
Preferably, in the step (1), the pressure of the rotary steaming is 0.1-0.2mPa, the temperature of the rotary steaming is 65-75 ℃, and the time of the rotary steaming is 2-6h.
Preferably, in step (1), the white solid is washed with acetone.
Preferably, in step (1), the solvent for recrystallization is an absolute ethanol-ethyl acetate mixed aqueous solution.
Further preferably, the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate contains 50-75 wt% of absolute ethyl alcohol, and the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate contains 10-15 wt% of ethyl acetate.
Further preferably, the number of times of recrystallization is 2 to 3.
Preferably, in step (2), the aqueous ethanol solution contains 60 wt% ethanol.
Preferably, in the step (2), the specific surface area of the hydrophilic white carbon black is 200-400m 2 /g。
Preferably, in step (2), the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane and/or vinyltris (2-methoxyethoxy) silane.
In a second aspect, the present invention provides a polymeric microsphere prepared by the above method.
The third aspect of the invention provides an application of the polymer microsphere in gardenia yellow dye dyeing.
The polymer microsphere prepared by the method can be combined with gardenia yellow dye, so that the ageing resistance of the dye is greatly improved, and indexes such as brightness, light fastness, water fastness and the like are improved to a certain extent after dyeing.
Drawings
FIG. 1 is an infrared spectrum of a silicon-based cationic monomer prepared in step (1) of example 1 of the present invention;
FIG. 2 is an infrared spectrum of the modified white carbon black prepared in the step (2) of the embodiment 1 of the present invention;
FIG. 3 is an infrared spectrum of polymer microspheres and styrene microspheres prepared in example 1 of the present invention;
FIG. 4 is an SEM image of polymer microspheres prepared according to example 1 of the invention;
FIG. 5 is a graph showing the particle size distribution of polymer microspheres produced in example 1 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing polymeric microspheres, comprising the steps of:
(1) Stirring and mixing silicon-containing methylamine, chloropropene and absolute ethyl alcohol, heating to 40-55 ℃ under nitrogen atmosphere for reaction for 24-30h, performing reduced pressure rotary evaporation to remove small molecular low-boiling substances to obtain yellow transparent liquid, cooling to obtain white solid, and sequentially washing, recrystallizing, performing reduced pressure suction filtration and vacuum drying on the white solid to obtain silicon-type cationic monomer;
(2) Adding hydrophilic white carbon black into an ethanol water solution, wherein the weight ratio of the hydrophilic white carbon black to the ethanol water solution is 1: (20-50), stirring and dispersing, then adding a silane coupling agent in a stirring state, heating to 100-120 ℃ for condensation and reflux, wherein the time of the condensation and reflux is 2.5-4h, cooling to room temperature after the condensation and reflux is finished, stopping stirring, washing by using toluene, and drying to obtain the modified white carbon black;
(3) Mixing styrene, N-tertiary butyl acrylamide, the silicon cationic monomer obtained in the step (1), the modified white carbon black obtained in the step (2), a cross-linking agent and 2,2' -azo (2-methylpropionamidine) dihydrochloride to obtain a mixture, adding water to obtain slurry, wherein the slurry contains 8-24 weight percent of the mixture, and then reacting for 2.5-8 hours at 80-95 ℃;
Wherein in step (1), the molar ratio of the silicon-containing methylamine to the chloropropene is 1: (2.7-3.3); the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the silicon-containing methylamine and the weight of the chloropropene is (1.05-1.1): 1, a step of;
in the step (2), the weight ratio of the silane coupling agent to the hydrophilic white carbon black is (0.05-0.2): 1;
in the step (3), the cross-linking agent is at least one of dimethyl diallyl ammonium chloride, N-methylene bisacrylamide and N-methylolacrylamide;
the weight ratio of the N-tertiary butyl acrylamide to the silicon cationic monomer to the modified white carbon black to the styrene is (0.15-0.35): (0.02-0.08): (0.005-0.03): 1, a step of;
the ratio of the weight of the cross-linking agent to the sum of the weights of the styrene, the N-tertiary butyl acrylamide, the silicon cation monomer and the modified white carbon black is (0.002-0.01): 1;
the ratio of the weight of the 2,2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of the styrene, the N-t-butyl acrylamide, the silicon type cationic monomer and the modified white carbon black is (0.004-0.02): 1.
in the present invention, in the step (1), the silicon-containing methylamine is at least one of N- (trimethylsilyl) dimethylamine, N- (trimethylsilyl) acetamide, and N, N-diethyltrimethylsilyl amine.
In a specific embodiment, in step (1), the molar ratio of the silicon-containing methylamine to the chloropropene may be 1:2.7, 1:2.8, 1:2.9, 1:3. 1:3.1, 1:3.2 or 1:3.3.
in a specific embodiment, in step (1), the ratio of the weight of the anhydrous ethanol to the sum of the weight of the silicon-containing methylamine and chloropropene may be 1.05: 1. 1.06: 1. 1.07: 1. 1.08: 1. 1.09:1 or 1.1:1.
in a specific embodiment, in step (1), the temperature of the reaction may be 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, or 55 ℃.
In particular embodiments, in step (1), the reaction time may be 24h, 24.5h, 25h, 25.5h, 26h, 26.5h, 27h, 27.5h, 28h, 28.5h, 29h, 29.5h, or 30h.
In the present invention, in step (1), the equipment used for the rotary steaming operation may be a conventional choice in the art. Preferably, the apparatus used for the rotary evaporation is a rotary evaporator.
In a preferred embodiment, in step (1), the pressure of the rotary evaporation is 0.1-0.2mPa, the temperature of the rotary evaporation is 65-75 ℃, and the time of the rotary evaporation is 2-6h. Specifically, the pressure of the spin-steaming may be 0.1mPa, 0.11mPa, 0.12mPa, 0.13mPa, 0.14mPa, 0.15mPa, 0.16mPa, 0.17mPa, 0.18mPa, 0.19mPa or 0.2mPa, the temperature of the spin-steaming may be 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, or 75 ℃, and the time of the spin-steaming may be 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours.
In the present invention, the pressure is a relative pressure.
In the present invention, in the step (1), the white solid is washed with acetone, and the number of times of washing is not particularly limited, and the unreacted raw material may be removed.
In the present invention, in step (1), the solvent for recrystallization is an absolute ethanol-ethyl acetate mixed aqueous solution.
In a preferred embodiment, the aqueous solution of the absolute ethyl alcohol-ethyl acetate mixture contains 50 to 75 weight percent of absolute ethyl alcohol, and the aqueous solution of the absolute ethyl alcohol-ethyl acetate mixture contains 10 to 15 weight percent of ethyl acetate. Specifically, the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate may contain 50 wt%, 52.5 wt%, 55 wt%, 57.5 wt%, 60 wt%, 62.5 wt%, 65 wt%, 67.5 wt%, 70 wt%, 72.5 wt% or 75 wt% of absolute ethyl alcohol, and the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate may contain 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt% or 15 wt% of ethyl acetate.
Preferably, the number of recrystallisation is from 2 to 3.
In the invention, in the step (1), there is no special requirement for the reduced pressure suction filtration, and the absolute ethyl alcohol-ethyl acetate mixed aqueous solution is completely pumped out.
In the present invention, in step (2), the aqueous ethanol solution contains 60% by weight of ethanol in step (2).
In a specific embodiment, in the step (2), the weight ratio of the hydrophilic white carbon black to the aqueous ethanol solution may be 1: 20. 1:22.5, 1: 25. 1:27.5, 1: 30. 1:32.5, 1: 35. 1:37.5, 1: 40. 1:42.5, 1: 45. 1:47.5 or 1:50.
in specific embodiments, in step (2), the weight ratio of the silane coupling agent to the hydrophilic white carbon black may be 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.17:1, 0.18:1, 0.19:1, or 0.2:1.
In a preferred embodiment, in the step (2), the hydrophilic white carbon black has a specific surface area of 200 to 400m 2 And/g. Specifically, the specific surface area of the hydrophilic white carbon black may be 200m 2 /g、300m 2 /g or 400m 2 /g。
Preferably, in step (2), the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane and/or vinyltris (2-methoxyethoxy) silane.
In a specific embodiment, in step (2), the temperature of the condensed reflux may be 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, or 120 ℃.
In specific embodiments, in step (2), the time of the condensed reflux may be 2.5h, 2.75h, 3h, 3.25h, 3.5h, 3.75h, or 4h.
In the invention, in the step (2), there is no special requirement on the number of times of toluene washing, and the unreacted hydrophilic white carbon black is completely absorbed.
In the present invention, the 2,2' -azo (2-methylpropionamidine) dihydrochloride is used as a cationic initiator.
In a specific embodiment, in step (3), the weight ratio of the N-t-butyl acrylamide to the styrene may be 0.15: 1. 0.16: 1. 0.17: 1. 0.18: 1. 0.19: 1. 0.2: 1. 0.21: 1. 0.22: 1. 0.23: 1. 0.24: 1. 0.25: 1. 0.26: 1. 0.27: 1. 0.28: 1. 0.29: 1. 0.3: 1. 0.31: 1. 0.32: 1. 0.33: 1. 0.34:1 or 0.35:1.
in a specific embodiment, in step (3), the weight ratio of the silicon-based cationic monomer to the styrene may be 0.02: 1. 0.025: 1. 0.03: 1. 0.035: 1. 0.04: 1. 0.045: 1. 0.05: 1. 0.055: 1. 0.06: 1. 0.065: 1. 0.07: 1. 0.075:1 or 0.08:1.
In a specific embodiment, in the step (3), the weight ratio of the modified white carbon black to the styrene may be 0.005: 1. 0.01:1. 0.015: 1. 0.02:1. 0.025:1 or 0.03:1.
in a specific embodiment, in the step (3), the ratio of the weight of the crosslinking agent to the sum of the weights of the styrene, the N-t-butyl acrylamide, the silicon-based cationic monomer, and the modified white carbon black may be 0.002: 1. 0.003: 1. 0.004: 1. 0.005: 1. 0.006: 1. 0.007: 1. 0.008: 1. 0.009:1 or 0.01:1.
in a specific embodiment, in step (3), the ratio of the weight of the 2,2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of the styrene, N-t-butyl acrylamide, silicon based cationic monomer and modified white carbon black may be 0.004: 1. 0.006: 1. 0.008: 1. 0.01:1. 0.012: 1. 0.014: 1. 0.016: 1. 0.018:1 or 0.02:1.
in particular embodiments, in step (3), the slurry may comprise 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, or 24 wt% of the blend.
In a specific embodiment, in step (3), the temperature of the reaction may be 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, or 95 ℃.
In specific embodiments, in step (3), the reaction time may be 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, or 8h.
In a second aspect, the present invention provides a polymeric microsphere prepared by the above method.
The third aspect of the invention provides an application of the polymer microsphere in gardenia yellow dye dyeing.
The fourth aspect of the invention provides a method for dyeing gardenia yellow dye, which is a direct dyeing method, a magnetron sputtering jet printing method or a direct jet printing method.
The method uses the hydrolyzed silane coupling agent to modify the white carbon black, can improve the easy agglomeration phenomenon of the white carbon black, and the modified white carbon black can carry out surface modification treatment on gardenia yellow dye.
The present invention will be described in detail by way of examples, but the method of the present invention is not limited thereto.
Example 1
(1) Is provided with a stirrer, a thermometer, a reflux condenser (a calcium chloride drying pipe is arranged at the upper end) and N 2 Adding 11.727g N- (trimethylsilyl) dimethylamine and 22.956g chloropropene (the molar ratio of N- (trimethylsilyl) dimethylamine to chloropropene is 1:3) into a dry four-neck flask of a protection device, adding 37.4576g absolute ethyl alcohol, uniformly mixing under electric stirring (the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the N- (trimethylsilyl) dimethylamine and the weight of the chloropropene is 1.08:1), then introducing nitrogen, heating to 45 ℃ under nitrogen atmosphere for reaction for 24h, then performing reduced pressure rotary evaporation (the rotary evaporation pressure is 0.11mPa, the rotary evaporation temperature is 72 ℃ for 5 h) by using a rotary evaporator to remove small molecular low-boiling substances to obtain yellow transparent liquid, then cooling in a refrigerator to obtain white solid, rapidly washing the white solid with acetone for a plurality of times, removing a small amount of unreacted raw materials, then recrystallizing by using an absolute ethyl alcohol-ethyl acetate mixed aqueous solution (the absolute ethyl acetate mixed aqueous solution contains 70 wt% absolute ethyl alcohol, the absolute ethyl acetate mixed aqueous solution contains ethanol-12 wt% of ethyl acetate), and then performing vacuum filtration on the aqueous solution of the absolute ethyl acetate, and drying the aqueous solution to obtain cationic ethyl acetate, and then performing vacuum filtration on the aqueous solution, and drying the aqueous solution of the aqueous solution;
(2) 1g of hydrophilic white carbon black (specific surface area 200m 2 Slowly adding 40g of ethanol water solution (the ethanol water solution contains 60 weight percent of ethanol, and the weight ratio of the hydrophilic white carbon black to the ethanol water solution is 1:40 After being stirred uniformly, the mixture is transferred into a three-neck flask, the mixture is stirred rapidly by a magnetic stirrer, after being dispersed completely, then 0.1g of silane coupling agent (gamma-methacryloxypropyl trimethoxysilane) is dripped in the stirring state, the temperature is raised to 110 ℃, the condensation reflux is carried out by a condensation tube, the time of the condensation reflux is 3 hours, the mixture is cooled to room temperature after the condensation reflux is finished, the stirring is stopped, the materials in the three-neck flask are taken out, and then toluene is used for carrying out the materialWashing and then drying to obtain modified white carbon black, wherein the weight ratio of the silane coupling agent to the hydrophilic white carbon black is 0.1:1;
(3) 10g of styrene, 2g of N-t-butyl acrylamide, 0.2g of the silicon-based cationic monomer obtained in the step (1), 0.05g of the modified white carbon black obtained in the step (2), 0.0368g of a crosslinking agent (dimethyl diallyl ammonium chloride) and 0.0735g of 2,2' -azo (2-methylpropionamidine) dihydrochloride are mixed to obtain a mixture, and 110g of ultrapure water is added to obtain a slurry, wherein the weight ratio of the N-t-butyl acrylamide, the silicon-based cationic monomer, the modified white carbon black and the styrene is 0.2:0.02:0.005:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon cationic monomer and modified white carbon black is 0.003: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.006:1, the slurry contains 10.1 weight percent of the mixture, and then the mixture is reacted for 4.5 hours at 82 ℃ to obtain the polymer microsphere A1.
Example 2
(1) Is provided with a stirrer, a thermometer, a reflux condenser (a calcium chloride drying pipe is arranged at the upper end) and N 2 11.727g N- (trimethylsilyl) dimethylamine and 20.660g chloropropene (the molar ratio of N- (trimethylsilyl) dimethylamine to chloropropene is 1:2.7) are added into a dry four-neck flask of a protection device, 34.0064g absolute ethyl alcohol is then added, the mixture is uniformly mixed under electric stirring (the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the N- (trimethylsilyl) dimethylamine and the weight of the chloropropene is 1.05:1), then nitrogen is introduced into the four-neck flask, the mixture is heated to 40 ℃ for reaction for 30h under the atmosphere of nitrogen, then reduced pressure rotary evaporation (the rotary evaporation pressure is 0.14mpa, the rotary evaporation temperature is 65 ℃ and the rotary evaporation time is 3.5 h) is carried out to remove small molecular low matters to obtain yellow transparent liquid, then the yellow transparent liquid is cooled in a refrigerator to obtain white solid, the white solid is quickly washed by acetone for a plurality of times, a small amount of unreacted raw materials are removed, and then the absolute ethyl alcohol-ethyl acetate mixed aqueous solution is used for recrystallization (the absolute ethyl alcohol-ethyl acetate mixed aqueous solution contains 75% absolute ethyl acetate, and the absolute ethyl acetate mixed aqueous solution is boiled)The solution contains 10 percent of ethyl acetate by weight), recrystallizing for 3 times, then carrying out vacuum filtration to remove the absolute ethyl alcohol-ethyl acetate mixed aqueous solution, and then carrying out vacuum drying to obtain the silicon cationic monomer;
(2) 1.5g of hydrophilic white carbon black (specific surface area 200m 2 /g) was slowly added to 67.5g of an aqueous ethanol solution (the aqueous ethanol solution contains 60 wt% ethanol, and the mass ratio of the hydrophilic white carbon black to the aqueous ethanol solution is 1:45 After being stirred uniformly, the mixture is transferred into a three-neck flask, the mixture is stirred rapidly by a magnetic stirrer, after the mixture is dispersed completely, then 0.15g of silane coupling agent (vinyl tri (2-methoxyethoxy) silane) is dripped under the stirring state, the temperature is raised to 100 ℃, the condensation reflux is carried out by a condensation pipe for 4 hours, the condensation reflux is cooled to room temperature after the condensation reflux is finished, the stirring is stopped, the materials in the three-neck flask are taken out, then toluene is used for washing the materials, and then the materials are dried to obtain the modified white carbon black, wherein the weight ratio of the silane coupling agent to the hydrophilic white carbon black is 0.1:1;
(3) 10g of styrene, 3g of N-t-butyl acrylamide, 0.5g of the silicon-based cationic monomer obtained in the step (1), 0.12g of the modified white carbon black obtained in the step (2), 0.0681g of a cross-linking agent (N, N-methylenebisacrylamide) and 0.1362g of 2,2' -azo (2-methylpropionamidine) dihydrochloride were mixed to obtain a mixture, and then 101g of ultrapure water was added to obtain a slurry, wherein the weight ratio of the N-t-butyl acrylamide, the silicon-based cationic monomer, the modified white carbon black and the styrene is 0.3:0.05:0.012:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon cation monomer and modified white carbon black is 0.005: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.01:1, the slurry contains 12.04 weight percent of the mixture, and then the mixture is reacted for 6 hours at 84 ℃ to obtain the polymer microsphere A2.
Example 3
(1) Is provided with a stirrer, a thermometer, a reflux condenser (a calcium chloride drying pipe is arranged at the upper end) and N 2 11.727g N- (trimethylsilyl) dimethylamine and a dry four-necked flask of the protection device were added25.251g of chloropropene (the molar ratio of N- (trimethylsilyl) dimethylamine to chloropropene is 1:3.3), then 40.6758g of absolute ethyl alcohol is added, the mixture is uniformly mixed under electric stirring (the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of N- (trimethylsilyl) dimethylamine and the weight of chloropropene is 1.1:1), then nitrogen is introduced, the mixture is heated to 46 ℃ under the atmosphere of nitrogen for 24.5h, then reduced pressure rotary evaporation is carried out by a rotary evaporator (the rotary evaporation pressure is 0.15mpa, the rotary evaporation temperature is 70 ℃ for 3 h), the small molecular low-boiling substances are removed to obtain yellow transparent liquid, then the yellow transparent liquid is cooled in a refrigerator, the white solid is quickly washed by acetone for a plurality of times, a small amount of unreacted raw materials are removed, then the mixture is recrystallized by an absolute ethyl alcohol-ethyl acetate mixed aqueous solution (the absolute ethyl alcohol containing 55% of weight in the absolute ethyl alcohol-ethyl acetate mixed aqueous solution), the absolute ethyl alcohol-ethyl acetate mixed aqueous solution containing 13% of weight of ethyl acetate is recrystallized for 2 times, the mixture is pumped out, and then the aqueous solution of the cationic ethyl acetate is dried under reduced pressure, and the aqueous solution of the cationic ethyl acetate is obtained;
(2) 2g of hydrophilic white carbon black (specific surface area 400m 2 Slowly adding 70g of ethanol water solution (the ethanol water solution contains 60 weight percent of ethanol, and the mass ratio of the hydrophilic white carbon black to the ethanol water solution is 1:35 After being stirred uniformly, the mixture is transferred into a three-neck flask, the mixture is stirred rapidly by a magnetic stirrer, after being dispersed completely, then 0.4g of silane coupling agent (gamma-methacryloxypropyl trimethoxysilane) is dripped in the stirring state, the temperature is raised to 105 ℃, the condensation reflux is carried out by a condensation pipe for 3.5h, the condensation reflux is cooled to room temperature after the condensation reflux is finished, the stirring is stopped, the materials in the three-neck flask are taken out, then toluene is used for washing the materials, and then the modified white carbon black is obtained by drying, wherein the weight ratio of the silane coupling agent to the hydrophilic white carbon black is 0.2:1;
(3) 10g of styrene, 3.5g of N-t-butyl acrylamide, 0.8g of the silicon-based cationic monomer obtained in the step (1), 0.3g of the modified white carbon black obtained in the step (2), 0.0876g of a cross-linking agent (N-methylolacrylamide) and 0.1752g of 2,2' -azo (2-methylpropionamidine) dihydrochloride are mixed to obtain a mixture, and 67.7g of ultrapure water is added to obtain a slurry, wherein the weight ratio of the N-t-butyl acrylamide, the silicon-based cationic monomer, the modified white carbon black and the styrene is 0.35:0.08:0.03:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon cation monomer and modified white carbon black is 0.006: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.012:1, the slurry contains 18 weight percent of the mixture, and then the mixture is reacted for 8 hours at 80 ℃ to obtain the polymer microsphere A3.
Example 4
(1) Is provided with a stirrer, a thermometer, a reflux condenser (a calcium chloride drying pipe is arranged at the upper end) and N 2 Adding 11.727g N- (trimethylsilyl) dimethylamine and 23.721g chloropropene (the molar ratio of N- (trimethylsilyl) dimethylamine to chloropropene is 1:3.1) into a dry four-neck flask of a protection device, adding 37.2204g absolute ethyl alcohol, uniformly mixing under electric stirring (the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the N- (trimethylsilyl) dimethylamine and the weight of the chloropropene is 1.05:1), introducing nitrogen, heating to 55 ℃ under the nitrogen atmosphere for reaction for 24h, performing reduced pressure rotary evaporation (the rotary evaporation pressure is 0.18mpa, the rotary evaporation temperature is 75 ℃ for 2 h) by using a rotary evaporator to remove small molecular low-boiling substances to obtain yellow transparent liquid, then cooling in a refrigerator to obtain white solid, quickly washing the white solid with acetone for several times, removing a small amount of unreacted raw materials, then recrystallizing by using an absolute ethyl alcohol-ethyl acetate mixed solvent (the absolute ethyl alcohol-ethyl acetate mixed solution contains 68 wt% absolute ethyl alcohol, the absolute ethyl alcohol-ethyl acetate mixed solution contains 14% absolute ethyl acetate, and then performing vacuum filtration on the mixed solution to obtain cationic ethyl acetate, and drying the aqueous solution under reduced pressure to obtain cationic ethyl acetate;
(2) 1.6g of hydrophilic white carbon black (specific surface area 200m 2 Slowly adding 72g of ethanol water solution (the ethanol water solution contains 60 weight percent of ethanol, and the mass ratio of the hydrophilic white carbon black to the ethanol water solution is 1:45 After being stirred evenly, the mixture is transferred into a three-neck flaskRapidly stirring by using a magnetic stirrer, dispersing completely, then dropwise adding 0.256g of silane coupling agent (gamma-methacryloxypropyl trimethoxysilane) in a stirring state, heating to 120 ℃, performing condensation reflux by using a condensation pipe for 2.5h, cooling to room temperature after the condensation reflux is finished, stopping stirring, taking out materials in a three-neck flask, washing the materials by using toluene, and drying to obtain modified white carbon black, wherein the weight ratio of the silane coupling agent to the hydrophilic white carbon black is 0.16:1;
(3) 10g of styrene, 2.8g of N-t-butyl acrylamide, 0.75g of the silicon-based cationic monomer obtained in the step (1), 0.24g of the modified white carbon black obtained in the step (2), 0.1379g of a crosslinking agent (dimethyldiallylammonium chloride, N-methylenebisacrylamide and N-methylolacrylamide) and 0.2758g of 2,2' -azo (2-methylpropionamidine) dihydrochloride were mixed to obtain a mixture, and 77.7g of ultrapure water was added to obtain a slurry, wherein the weight ratio of N-t-butyl acrylamide, the silicon-based cationic monomer, the modified white carbon black and the styrene was 0.28:0.075:0.024:1, the ratio of the weight of the cross-linking agent to the sum of the weight of the styrene, the N-tertiary butyl acrylamide, the silicon cationic monomer and the modified white carbon black is 0.01: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.02:1, the slurry contains 15.45 weight percent of the mixture, and then the mixture is reacted for 2.5 hours at the temperature of 95 ℃ to obtain the polymer microsphere A4.
Comparative example 1
The procedure of example 2 was followed, except that in step (1), 11.727g N- (trimethylsilyl) dimethylamine and 15.304g chloropropene were added to a dry four-necked flask, and 28.3826g of absolute ethanol, i.e., N- (trimethylsilyl) dimethylamine to chloropropene in a molar ratio of 1:2, the ratio of the weight of absolute ethanol to the sum of the weights of N- (trimethylsilyl) dimethylamine and chloropropene is 1.05:1 to obtain polymer microsphere D1.
Comparative example 2
The procedure described in example 3 was followed, except that in step (1), 11.727g N- (trimethylsilyl) dimethylamine and 30.608g chloropropene were added to a dry four-necked flask, and 46.5685g of absolute ethanol, i.e., N- (trimethylsilyl) dimethylamine to chloropropene in a molar ratio of 1:4, the ratio of the weight of absolute ethanol to the sum of the weights of N- (trimethylsilyl) dimethylamine and chloropropene is 1.1:1 to obtain polymer microsphere D2.
Comparative example 3
The process of example 2 was carried out, except that in step (2), the amount of the silane-based coupling agent used was 0.015g, i.e., the weight ratio of the silane-based coupling agent to the hydrophilic white carbon black was 0.01:1, to obtain polymer microsphere D3.
Comparative example 4
The process of example 3 was carried out, except that in step (2), the amount of the silane coupling agent used was 0.6g, i.e., the weight ratio of the silane coupling agent to the hydrophilic white carbon black was 0.3:1, to obtain polymer microsphere D4.
Comparative example 5
The process was carried out as described in example 1, except that in step (3), 10g of styrene, 0.5g of N-t-butylacrylamide, 0.6g of the silicon-based cationic monomer obtained in step (1), 0.2g of the modified white carbon black obtained in step (2), 0.0904g of a crosslinking agent (dimethyldiallylammonium chloride) and 0.1808g of 2,2' -azo (2-methylpropionamidine) dihydrochloride were mixed to obtain a mixture, and 110g of ultrapure water was added to obtain a slurry, i.e., the weight ratio of N-t-butylacrylamide, silicon-based cationic monomer, modified white carbon black and styrene was 0.05:0.06:0.02:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon type cationic monomer and modified white carbon black is 0.008: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon based cationic monomer and modified white carbon black was 0.016:1, the slurry contained 9.52 wt% of the mixture, to obtain polymer microsphere D5.
Comparative example 6
The process of example 1 was carried out, except that in step (3), 10g of styrene, 5g of N-t-butylacrylamide, 0.4g of the silicon-based cationic monomer obtained in step (1), 0.15g of the modified white carbon black obtained in step (2), 0.1088g of the crosslinking agent (dimethyldiallylammonium chloride) and 0.2177g of 2,2' -azo (2-methylpropylamide) dihydrochloride were mixed, and 110g of ultrapure water was added to obtain a slurry, i.e., the weight ratio of N-t-butylacrylamide, silicon-based cationic monomer, modified white carbon black to styrene was 0.5:0.04:0.015:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black is 0.007: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon based cationic monomer and modified white carbon black was 0.014:1, the slurry contained 12.61 wt% of the mixture to obtain polymer microspheres D6.
Comparative example 7
The process was carried out as described in example 1, except that in step (3), 10g of styrene, 3g of N-t-butylacrylamide, 0.1g of the silicon-based cationic monomer obtained in step (1), 0.3g of the modified white carbon black obtained in step (2), 0.067g of a crosslinking agent (dimethyldiallylammonium chloride) and 0.134g of 2,2' -azo (2-methylpropylamide) dihydrochloride were mixed, and 110g of ultrapure water was added to obtain a slurry, i.e., the weight ratio of N-t-butylacrylamide, silicon-based cationic monomer, modified white carbon black to styrene was 0.3:0.01:0.03:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon cation monomer and modified white carbon black is 0.005: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.01:1, the slurry contains 11 wt% of the mixture to polymer microsphere D7.
Comparative example 8
The process of example 1 was carried out, except that in step (3), 10g of styrene, 3.5g of N-t-butyl acrylamide, 1g of the silicon-based cationic monomer obtained in step (1), 0.05g of the modified white carbon black obtained in step (2), 0.1164g of a crosslinking agent (dimethyldiallylammonium chloride) and 0.2328g of 2,2' -azo (2-methylpropylamidine) dihydrochloride were mixed, and 110g of ultrapure water was added to obtain a slurry, namely, N-t-butyl acrylamide, silicon-based cationic monomer, modified white carbon black and styrene in a weight ratio of 0.35:0.1:0.005:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon type cationic monomer and modified white carbon black is 0.008: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon based cationic monomer and modified white carbon black was 0.016:1, the slurry contained 11.93 wt% of the mixture, to obtain polymer microsphere D8.
Comparative example 9
The process of example 1 was carried out, except that in step (3), 10g of styrene, 2g of N-t-butylacrylamide, 0.4g of the silicon-based cationic monomer obtained in step (1), 0.04g of the modified white carbon black obtained in step (2), 0.063g of a crosslinking agent (dimethyldiallylammonium chloride) and 0.126g of 2,2' -azo (2-methylpropylamide) dihydrochloride were mixed, and 110g of ultrapure water was added to obtain a slurry, i.e., the weight ratio of N-t-butylacrylamide, silicon-based cationic monomer, modified white carbon black to styrene was 0.2:0.04:0.004:1, the ratio of the weight of the crosslinking agent to the sum of the weights of styrene, N-t-butyl acrylamide, silicon based cationic monomer and modified white carbon black was 0.0051: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.01:1, the slurry contained 10.3 wt% of the mixture to obtain polymer microsphere D9.
Comparative example 10
The process of example 1 was carried out, except that in step (3), 10g of styrene, 1.5g of N-t-butylacrylamide, 0.5g of the silicon-based cationic monomer obtained in step (1), 0.6g of the modified white carbon black obtained in step (2), 0.0756g of the crosslinking agent (dimethyldiallylammonium chloride) and 0.1512g of 2,2' -azo (2-methylpropylamidine) dihydrochloride were mixed, and 110g of ultrapure water was added to obtain a slurry, i.e., the weight ratio of N-t-butylacrylamide, silicon-based cationic monomer, modified white carbon black and styrene was 0.15:0.05:0.06:1, the ratio of the weight of the cross-linking agent to the sum of the weights of styrene, N-tertiary butyl acrylamide, silicon cation monomer and modified white carbon black is 0.006: the ratio of the weight of 1, 2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of styrene, N-t-butyl acrylamide, silicon type cationic monomer and modified white carbon black was 0.012:1, the slurry contained 10.44 wt% of the mixture to obtain polymer microsphere D10.
Test example 1
The silicon type cationic monomer obtained in the step (1) of the example 1 is detected by a Fourier transform infrared spectrometer, as shown in FIG. 1, wherein 1440-1400cm of the cationic monomer is shown in FIG. 1 -1 In-plane deformation vibration of 1355cm -1 Is deformed and vibrated symmetrically of 1021cm -1 The stretching vibration peak of (C) shows the structure of quaternary ammonium salt and CH 3 The presence of a Cl bond and of a Si-O bond, the silicon-based cationic monomer obtained in example 1 was dimethyl trimethylsilylallyl ammonium chloride.
Test example 2
The modified white carbon black obtained in the step (2) of example 1 was examined by a Fourier transform infrared spectrometer, as shown in FIG. 2, and as shown in FIG. 2, the modified white carbon black was obtained by 3452cm -1 The wide absorption peak is structural hydrated hydroxyl-OH antisymmetric telescopic vibration peak in hydrophilic white carbon black, at 2366 and 2321cm -1 The vibration peak of-Si-H stretching indicates the existence of white carbon black. 1095cm -1 The strong absorption peak is Si-O-Si antisymmetric telescopic vibration peak 768cm -1 The Si-O symmetrical telescopic vibration peak can indicate that the coupling agent is hydrolyzed and reacts with the hydrophilic white carbon black.
2975cm -1 Is the stretching vibration peak of-CH on aliphatic unsaturated diene bond, which corresponds to the existence of vinyl in KH570, 1600cm -1 The strong absorption peak is an acyloxy o=c-O-stretching vibration peak, and the existence of an acryloyloxy group in KH570 further indicates that the bonding reaction between KH570 and white carbon black exists.
Test example 3
As shown in FIG. 3, A1 and styrene microspheres were detected by a Fourier transform infrared spectrometer, and FIG. 3 shows that A1 was compared with pure styrene microspheres, A1 was at 2927cm -1 、1385cm -1 And 1021cm -1 Corresponds to the expansion and contraction vibration of A1 microsphere(CH 2 ) n Chain structure, -C- (CH) 3 ) 3 Characteristic peaks of tert-butyl and-Si-O-Si-bond, 1590cm -1 In-plane deformation vibration occurs, corresponding to the quaternary ammonium salt structure in A1.
Test example 4
The morphology of A1 was examined by scanning electron microscopy, as shown in FIG. 4, and the spherical particles of A1 were of a uniform size and have an average particle diameter of about 100-200nm from FIG. 4.
Test example 5
The particle size distribution of A1 was measured by a Markov particle size analyzer, and as shown in FIG. 5, the particle size distribution was good from FIG. 5, and the average particle size was about 110 nm.
Test example 6
The A1-A4 and the D1-D10 are respectively adsorbed with gardenia yellow dye (the brand of the gardenia yellow dye is alpha-crocin, the chromatographic grade is purchased from Aba Ding Shiji company), and then cotton fabric is dyed, and the adsorption and dyeing process is as follows:
(1) The dye adsorption process of the polymer microsphere comprises the following steps: adding deionized water into polymer microspheres, performing ultrasonic dispersion for 10min to obtain 10 wt% concentration polymer microsphere emulsion, taking 10g of 10 wt% concentration polymer microsphere emulsion, mixing with 1.6mL of gardenia Huang Ranye (the concentration of gardenia yellow dye in gardenia yellow dye liquor is 2-20 g/L), adding deionized water to a volume of 100mL, adjusting pH to 7-8, performing heat preservation at 40 ℃ for 60min in a constant temperature mixer, centrifuging the obtained emulsion, controlling the rotation speed to 10000 revolutions per minute, taking the lower precipitate, sequentially flushing with 20mL of acetone and 20mL of deionized water, centrifuging (the rotation speed is 10000 revolutions per minute, and the centrifuging time is 10 min), and repeating the flushing and centrifuging steps to freeze-dry the obtained purified precipitate to obtain the gardenia microsphere powder;
(2) The gardenia microsphere dyeing process comprises the following steps: taking 50mg of the gardenia microsphere powder obtained in the step (1), adding deionized water, performing ultrasonic dispersion for 10min to obtain 100ml of gardenia microsphere dye liquor, adding 2g of pure cotton white cloth, dyeing at 20-40 ℃ for 30min, and sequentially performing water washing, neutral soaping and drying to obtain dyed cotton fabric.
Respectively detecting the ageing resistance of the A1-A4 and the D1-D10 after adsorbing the gardenia yellow dye and the ageing resistance of the gardenia yellow dye which is not adsorbed by the polymer microspheres;
the ageing resistance test method comprises the following steps:
50mg of gardenia microsphere powder prepared in the adsorption and dyeing process step (1) is respectively taken from A1 to A4 and D1 to D10 (at the moment, the concentration of gardenia yellow dye in the gardenia yellow dye liquid used in the step (1) is 8g/L, the pH value is 8), deionized water is added, ultrasonic dispersion is carried out for 10min, 100ml of gardenia microsphere dye liquid is obtained, and the aging resistance of the gardenia microsphere dye liquid is measured.
The same pigment is irradiated under different optical filters, the quantum yield is different, and the reaction intensity is different. The wavelength of the irradiation light is controlled by using an optical filter, and the influence of different color lights on the stability of the yellow light of the gardenia is analyzed. The dye solutions of the gardenia microspheres prepared by the volumes A1-A4 and D1-D10 with the volume of 20mL and the gardenia Huang Ranye which is not adsorbed by the polymer microspheres and has the concentration of 0.64mg/100mL (at the moment, the dye solution of the gardenia yellow with the volume of 0.128mg is contained in the dye solution of the gardenia yellow with the volume of 20mLA1-A4, and the weight of the dye solution of the gardenia yellow in the dye solution of the gardenia microsphere) are respectively taken and placed in a culture dish (phi=12 cm), and the culture dish is placed in sunlight for equidistant irradiation, and is respectively added with red, blue filters and white glass sheets to ensure the wavelength range. The volume of the pigment solution in the culture dish was 10ml, and the initial absorbance was 1. 5ml was taken out every 12h to a constant volume of 50ml and absorbance was measured at λ=460 nm. And taking absorbance after 240h illumination as an anti-aging judgment basis.
The results are shown in Table 1
TABLE 1
As shown in Table 1, the polymer microsphere obtained by the invention has an aging resistance of > 0 after adsorbing gardenia yellow dye.35h -1 The ageing resistance of the blue tablet is more than 0.25h -1 The ageing resistance of the white tablet is more than 0.2h -1 The polymer microsphere obtained by the method can greatly improve the ageing resistance of the dye.
Respectively detecting the brightness L, the light fastness, the water fastness and the K/S value of the dyed cotton fabric obtained by adopting the adsorption and dyeing process (at the moment, the concentration of the gardenia yellow dye in the gardenia yellow dye liquor used in the step (1) is 8g/L, and the pH value is 8);
to better illustrate the effect of the invention, a blank group is also arranged
Blank group
Adding deionized water into 0.64mg of gardenia yellow dye (the weight of the gardenia yellow dye in the gardenia microsphere dye liquor prepared in the adsorption and dyeing process step (2) of A1-A4) to obtain 100ml of gardenia Huang Ranye, adding 2g of pure cotton white cloth, dyeing for 30min at 20-40 ℃, and sequentially performing water washing, neutral soaping and drying to obtain dyed cotton fabric.
The brightness L and K/S value detection method of the dyed cotton fabric comprises the following steps: the fabric was measured using Datacolor-600, D65 light source, 10℃viewing angle. Folding each sample for 4 layers, measuring for 4 times at different positions, and taking an average value;
The light fastness detection method of the dyed cotton fabric comprises the following steps: respectively testing the light fastness of the fabric by referring to the standard of national standard GB/T14576-2009 "light fastness and sweat composite fastness for textile color fastness test";
the method for detecting the water fastness of the dyed cotton fabric comprises the following steps: the fastness to water immersion of the fabric is respectively tested by referring to the national standard GB/T5713-2013 "fastness to water of textiles".
The results are shown in tables 2-4
TABLE 2 (dyeing temperature 20 ℃ C.)
From the data in Table 2, the polymer microsphere obtained by the invention is used for dyeing cotton fabrics after adsorbing gardenia yellow dye, has softer brightness, has K/S of more than 0.6, has better light fastness and water fastness, and has larger improvement than a blank group. The polymer microsphere prepared by the method is proved to be obviously improved in apparent color yield (K/S is more than 0.6), light fastness and water fastness after being colored on the fabric after being adsorbed with gardenia yellow dye.
TABLE 3 (dyeing temperature 30 ℃ C.)
From the data in Table 3, the polymer microsphere obtained by the invention is used for dyeing cotton fabrics after adsorbing gardenia yellow dye, has softer brightness, has K/S of more than 0.55, has better light fastness and water fastness, and has larger improvement than that of a blank group. The polymer microsphere prepared by the method is proved to be obviously improved in apparent color yield (K/S is more than 0.55), light fastness and water fastness after being colored on the fabric after being adsorbed with gardenia yellow dye.
TABLE 4 (dyeing temperature 40 ℃ C.)
From the data in Table 4, the polymer microsphere obtained by the invention is used for dyeing cotton fabrics after adsorbing gardenia yellow dye, has softer brightness, has K/S of more than 0.6, has better light fastness and water fastness, and has larger improvement than that of a blank group. The polymer microsphere prepared by the method is proved to be obviously improved in apparent color yield (K/S is more than 0.6), light fastness and water fastness after being colored on the fabric after being adsorbed with gardenia yellow dye.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing polymer microspheres, comprising the steps of:
(1) Stirring and mixing silicon-containing methylamine, chloropropene and absolute ethyl alcohol, heating to 40-55 ℃ under nitrogen atmosphere for reaction for 24-30h, performing reduced pressure rotary evaporation to remove small molecular low-boiling substances to obtain yellow transparent liquid, cooling to obtain white solid, and sequentially washing, recrystallizing, performing reduced pressure suction filtration and vacuum drying on the white solid to obtain silicon-type cationic monomer;
(2) Adding hydrophilic white carbon black into an ethanol water solution, wherein the weight ratio of the hydrophilic white carbon black to the ethanol water solution is 1: (20-50), stirring and dispersing, then adding a silane coupling agent in a stirring state, heating to 100-120 ℃ for condensation and reflux, wherein the time of the condensation and reflux is 2.5-4h, cooling to room temperature after the condensation and reflux is finished, stopping stirring, washing by using toluene, and drying to obtain the modified white carbon black;
(3) Mixing styrene, N-tertiary butyl acrylamide, the silicon cationic monomer obtained in the step (1), the modified white carbon black obtained in the step (2), a cross-linking agent and 2,2' -azo (2-methylpropionamidine) dihydrochloride to obtain a mixture, adding water to obtain slurry, wherein the slurry contains 8-24 weight percent of the mixture, and then reacting for 2.5-8 hours at 80-95 ℃;
wherein in step (1), the molar ratio of the silicon-containing methylamine to the chloropropene is 1: (2.7-3.3); the ratio of the weight of the absolute ethyl alcohol to the sum of the weight of the silicon-containing methylamine and the weight of the chloropropene is (1.05-1.1): 1, a step of;
the silicon-containing methylamine is N- (trimethylsilyl) dimethylamine and/or N, N-diethyl trimethylsilyl amine;
In the step (2), the weight ratio of the silane coupling agent to the hydrophilic white carbon black is (0.05-0.2): 1;
in step (2), the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane and/or vinyl tris (2-methoxyethoxy) silane;
in the step (3), the cross-linking agent is at least one of dimethyl diallyl ammonium chloride, N-methylene bisacrylamide and N-methylolacrylamide;
the weight ratio of the N-tertiary butyl acrylamide, the silicon cationic monomer, the modified white carbon black and the styrene is (0.15-0.35): (0.02-0.08): (0.005-0.03): 1, a step of;
the ratio of the weight of the cross-linking agent to the sum of the weights of the styrene, the N-tertiary butyl acrylamide, the silicon cation monomer and the modified white carbon black is (0.002-0.01): 1;
the ratio of the weight of the 2,2' -azo (2-methylpropionamidine) dihydrochloride to the sum of the weights of the styrene, the N-t-butyl acrylamide, the silicon type cationic monomer and the modified white carbon black is (0.004-0.02): 1.
2. the method according to claim 1, wherein in step (1), the pressure of the rotary evaporation is 0.1-0.2mPa, the temperature of the rotary evaporation is 65-75 ℃, and the time of the rotary evaporation is 2-6h.
3. The process according to claim 1, characterized in that in step (1) the white solid is washed with acetone.
4. A process according to claim 1 or 3, wherein in step (1) the recrystallised solvent is an aqueous ethanol-ethyl acetate mixture.
5. The method according to claim 4, wherein in the step (1), the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate contains 50 to 75% by weight of absolute ethyl alcohol, and the mixed aqueous solution of absolute ethyl alcohol and ethyl acetate contains 10 to 15% by weight of ethyl acetate.
6. The method according to claim 4, wherein in the step (1), the number of times of recrystallization is 2 to 3.
7. The method according to claim 1, wherein in step (2), the aqueous ethanol solution contains 60% by weight of ethanol.
8. The method according to claim 1, wherein in the step (2), the hydrophilic white carbon black has a specific surface area of 200 to 400m 2 /g。
9. A polymeric microsphere prepared by the method of any one of claims 1-8.
10. Use of the polymeric microspheres of claim 9 for dyeing gardenia yellow dyes.
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