CN113980486A - Preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex - Google Patents
Preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex Download PDFInfo
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Abstract
The invention discloses a preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex, which comprises the following steps: synthesizing a chemical crosslinking type copolymer nano particle with the amphiphilic end active group particle size of 10-250nm by RAFT free radical polymerization induced self-assembly (PISA), and using the chemical crosslinking type copolymer nano particle to adsorb and disperse organic pigment particles. The chemical crosslinking type copolymer nano particle is used for regulating and controlling the in-situ soap-free RAFT emulsion polymerization of the film-forming hydrophobic monomer on the surface of the organic pigment to obtain the soap-free chemical crosslinking type copolymer nano particle coated organic pigment hybrid latex. The hybrid latex prepared by soap-free in-situ RAFT emulsion copolymerization has the characteristics of high latex stability, high pigment coating rate, clear coating polymer layer sequence, controllable structure and the like, and is suitable for surface coating modification of various pigments. Has the characteristics of small equipment investment, simple production process, stable product quality, suitability for large-scale production and the like.
Description
Technical Field
The invention relates to the field of capsule pigment coatings in fine chemical engineering, in particular to a preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex.
Background
The organic pigment has the advantages of strong tinting strength, bright color, complete color spectrum and the like, is widely applied to the industrial fields of printing ink printing, coating, plastics, rubber and the like, and becomes an indispensable coloring material for producing various industrial products. However, organic pigments are insoluble in water, and they are agglomerated together to form aggregates during synthesis and drying, and there is no affinity between the pigments and the textile, and generally, it is necessary to attach pigment particles to the fiber surface by means of film-forming substances such as binders to obtain a certain color fastness, which results in severe influence on the application properties, such as tinting strength, hiding power, transparency, etc. Therefore, before practical application, the organic pigment needs to be dispersed to prepare a stable dispersion with a particle size and distribution meeting certain requirements.
The surface of organic pigment is modified by adsorption by adopting surfactant, modifier, pigment derivative and the like, or the pigment is encapsulated by polymer or inorganic particles, which is the most common means for ultra-fining the pigment at present. The surface adsorption modification has the problems of complex process and residual dispersant, so the multifunctional polymer coated pigment ink can endow textile printed products with excellent fastness performance by virtue of low viscosity and excellent jettability, and is widely concerned by researchers.
The Chinese patent application No. 201010204005.8 discloses a method for preparing a micro-surface free radical polymerization superfine coated organic pigment, which comprises the steps of taking an organic pigment, a polymerizable dispersant, a nonionic emulsifier and deionized water as matrixes, preparing a superfine organic pigment water-based dispersion system by grinding, adding a monomer into the system, emulsifying at a high speed, and heating to initiate polymerization reaction to prepare the superfine polymer coated organic pigment. The superfine polymer coated organic pigment prepared by the method has the characteristics of small particle size, narrow particle size distribution, good dispersibility and high stability.
The Chinese patent application No. 201410403283.4 discloses an organic pigment water-based color paste for coloring viscose dope and a preparation method thereof, wherein a polymerizable emulsifier is used for miniemulsion polymerization to coat the polymer of the organic pigment, and the organic pigment water-based color paste prepared from the organic pigment coated by the polymer, a water-soluble organic solvent, a pH value regulator, a wetting agent, deionized water and the like has the characteristics of high storage stability and spinnability, spun color filaments and excellent soaping-resistant color fastness.
Pigment encapsulation is usually carried out by adding surface active substances such as emulsifiers. The traditional small molecular emulsifier is easy to desorb and migrate, so that the stability of the polymer latex is lost; on the other hand, the conventional emulsifier is easy to migrate in the adhesive film, and the physical properties of the adhesive film are affected. The chinese patent application No. 202010960365.4 discloses a method for synthesizing polymer/pigment hybrid latex by copolymerization of sulfur-free and soap-free in-situ RAFT emulsion, wherein a reactive emulsifier is selected to disperse a pigment to prepare a pigment dispersion. An amphiphilic sulfur-free-end omega-vinyl methacrylate macromolecule RAFT reagent is synthesized in situ on the surface of pigment particles by adopting a catalytic chain transfer polymerization method. And (3) dropwise adding an acrylate monomer, carrying out in-situ sulfur-free RAFT polymerization, and regulating and controlling the structure and composition of the coating polymer.
Nanoparticle emulsifiers have many advantages over traditional surfactant or polymer emulsifiers, including superior long-term emulsion stability and reduced foam during homogenization. At the turn of the last century, Ramsden and Pickering have found that various types of particles can stabilize emulsions.
The Chinese patent application with the application number of 202010506737.6 discloses a nano-material coated organic composite pigment and a preparation method thereof, wherein the nano-material coated organic pigment is prepared by a layer-by-layer self-assembly method of a nano-material and an organic pigment, and a protective layer is formed on the surface of the organic pigment in the form of an inorganic coated organic pigment, so that the internal organic pigment is better protected, and the prepared nano-material coated organic pigment has better alkali resistance and heat resistance, and also has the advantages of uniform color, strong pigment covering power and the like.
Although the inorganic nano material coated pigment improves the chemical stability of the pigment, the inorganic nano material coated pigment has natural defect on film forming performance. Aqueous polymer particles such as microgels, block copolymer nanoparticles, and the like provide a new approach. The polymerization induced self-assembly is characterized in that soluble macromolecular chain transfer agents or initiators are used as stabilizers, polymerization monomers generate macromolecular chain segments insoluble in a polymerization system, an amphiphilic block polymer is obtained, and the block polymer can be self-assembled into aggregates along with the growth of the insoluble chain segments in the polymerization process. The method can directly prepare the copolymer in the form of nano particles under the condition of high solid phase, and eliminates any requirement on post-polymerization processing. Depending on the monomer selection, colloidally stable nanoparticle dispersions can be obtained in water, ethanol or n-alkanes. Hunter S J et al reviewed the development of Pickering emulsifiers for polymerization-induced self-assembly (PISA) preparation of block copolymer nanoparticles [ Langmuir,2020,36(51) ]. Zhang Q et al reported a stable Pickering high internal phase emulsion of vermicular Polymer nanoaggregates prepared from PISA [ Polymer Chemistry,2017,8,5474 ]. Lotierzo a reports an example of the use of nanogels as stabilizers for emulsion polymerization [ ACS Nano,2019,13, 399-. There has been no report on the preparation of block copolymer nanoparticles as an example of an organic pigment emulsifier using a polymerization induced self-assembly method (PISA).
Disclosure of Invention
The invention aims to solve the technical problem of providing a soap-free chemical crosslinking type copolymer nanoparticle-coated organic pigment hybrid latex and a preparation method thereof, solving the problem that the stability of the latex is lost due to the fact that an emulsifier added in the traditional pigment encapsulation coating process is easy to desorb and migrate, and more importantly solving the problems that the coating rate of the existing multifunctional polymer-coated pigment is not high, the molecular structure is not controllable and the like. The invention adopts RAFT free radical polymerization induced self-assembly (PISA) to synthesize chemical crosslinking type copolymer nano particles for adsorbing and dispersing organic pigment particles. The saponification-free polymer/pigment hybrid latex is hopeful to be realized, and the coating rate and the dispersion stability of the organic pigment can be improved.
The invention relates to soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex and a preparation method thereof, wherein the soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex comprises the following steps:
(1) synthesizing a chemical crosslinking type copolymer nano particle with the amphiphilic end active group particle size of 10-250nm by RAFT free radical polymerization induced self-assembly (PISA), and using the chemical crosslinking type copolymer nano particle to adsorb and disperse organic pigment particles.
The synthesis steps are as follows: synthesizing the PISA copolymer nano particles by adopting a sulfur-containing and sulfur-free RAFT free radical polymerization mode. Firstly, synthesizing a water-soluble macromolecule RAFT reagent: in the traditional sulfur-containing RAFT polymerization, ACVA (azodicyano valeric acid) is used as an initiator, a small molecular RAFT reagent and a water-soluble monomer are added, a water-soluble macromolecular RAFT reagent is synthesized by RAFT solution polymerization, sulfur-free RAFT polymerization takes a cobalt complex as a catalyst, a catalytic chain transfer polymerization method is adopted to synthesize a sulfur-free terminal omega-vinyl macromolecular RAFT reagent on the surface of a pigment particle in situ, and petroleum ether is used for precipitation and purification.
Secondly, chain extension self-assembly of insoluble blocks: AIBN (azodiisobutyronitrile) is used as an initiator, a monomer which is insoluble in a system is subjected to chain extension through RAFT dispersion polymerization to generate a high molecular chain segment which is insoluble in a polymerization system, the polymer nano particle aggregate is self-assembled along with the growth of the chain segment, and a cross-linking agent is added during the particle synthesis to realize the covalent stability of the self-assembled aggregate.
(2) Mixing the chemically crosslinked copolymer nanoparticles with a pigment in a water system to generate a pigment dispersion liquid, wherein the chemically crosslinked copolymer nanoparticles are used for regulating and controlling the in-situ soap-free RAFT emulsion polymerization of a film-forming hydrophobic monomer on the surface of an organic pigment to obtain the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex.
The small molecular RAFT reagent adopted in the step (1) is a sulfur-containing RAFT reagent such as 4-cyano-4- (dodecyl sulfonyl thiocarbonyl) sulfonyl valeric acid (CDPA), 4-cyano-4- (propyl sulfonyl thiocarbonyl) sulfonyl valeric acid (CPP), 4-cyano-4- (propyl sulfonyl thiocarbonyl) sulfonyl valeric acid (CPDB), alpha-dithio naphthoic acid isobutyronitrile ester (CPDN) and the like; the cobalt complex is one or more of cobalt bis (boron difluoride phenylenedioxime) dihydrate and cobalt bis (boron difluoride phenylenedioxime) dihydrate, and the dosage of the cobalt complex is 80-120ppm of the mass of the water-soluble monomer.
The water-soluble macromolecule RAFT reagent adopted in the step (1) is PDMA or PEOx+1One or more of MA, PMAA, PGMA and PMMA, and the target polymerization degree is 10-100. In order to improve the strong adsorption capacity of the pigment particles, the water-soluble macromolecular RAFT unit comprises an ionic group, a carboxylic group, a nonionic group polyoxyethylene ether and the like to improve the electrostatic attraction and water phase dispersion performance of the coated pigment particles. DMA is cationic in the environment of pH less than 9, MAA ionizes carboxylic acid groups in the weakly acidic and alkaline environment to keep electrostatic stability, MMA and PEOx+1MA extremely hydrophilic, PEOx+1The MA side group has hydrophilic group polyoxyethylene ether.
The hydrophobic monomer adopted in the step (1) is BzOne of MA, MEA, HPMA and BA, and the target polymerization degree is 10-350.
The crosslinking monomers adopted in the step (1) are Ethylene Glycol Dimethacrylate (EGDMA) and trimethylolpropane trimethacrylate, and the target polymerization degree is 5-50. The addition of a cross-linking agent during particle synthesis effects covalent stabilization of the self-assembled aggregates, making them less susceptible to peeling under shear. The pendant trimethylolpropane trimethacrylate crosslinker contains vinyl groups, which render it reactive for subsequent emulsion polymerization of the pigment latex.
When the chemically cross-linked copolymer nanoparticles are synthesized by RAFT free radical polymerization induced self-assembly (PISA) in the step (1), self-assembled aggregates with different morphological structures, including micelles, nanowires, vesicles and the like, can be obtained according to the difference of the macromolecular RAFT reagents and the difference of the added hydrophobic monomers.
In the step (1), the molecular structural formula of the chemically cross-linked copolymer nanoparticle with the amphiphilic end active group particle size of 10-250nm is as follows:
a. in b, x is 7-18; n is 50-100; m is 100-350; z is 10-50; a: b: c is 50:30:20(mol: mol); a + b + c ═ n ═ 50 to 100;
c. in d, x is 7-18; n is 10-30; m is 10-80; z is 5-20; a: b: c is 50:30:20(mol: mol); a + b + c ═ n ═ 10-30;
the pigment dispersion liquid in the step (2) is prepared by firstly diluting the copolymer nanoparticle dispersion liquid in water, then adding the pigment, and performing ultrasonic homogenization to obtain the pigment dispersion liquid, wherein the pigment can be pigment red 170, titanium pigment, phthalocyanine blue pigment, benzidine yellow pigment and the like. The pigment dispersion liquid is prepared by adopting various pigments, and the wide applicability of the soap-free in-situ RAFT emulsion copolymerization synthesized polymer/pigment hybrid latex is verified.
The mass concentration ratio of the chemical crosslinking copolymer nano particles/pigments to be adsorbed and dispersed in the step (2) is 0.25-10.
The in-situ control of the structure of the coating layer polymer in the step (2) can be realized by sequentially dripping acrylate monomers for RAFT polymerization. Adding an aqueous solution of acrylic ester monomers and water-soluble initiators which are subjected to oxygen discharge treatment in advance in an injection mode, wherein the volume of the added aqueous solution of the initiators is equal to the volume of the monomers, and the feeding speed is 0.02-10 mL/min.
The film-forming hydrophobic monomer adopted in the step (2) adopts a combination of a hard monomer and a soft monomer, wherein the hard monomer is Methyl Methacrylate (MMA), isobutyl methacrylate (IBMA) or benzyl methacrylate (BzMA), and the soft monomer is Butyl Methacrylate (BMA) or Butyl Acrylate (BA).
And (3) sequentially dripping acrylate monomers in the step (2), synthesizing a polymer coated organic pigment with a controllable structure, and obtaining the polymer/organic pigment hybrid latex with the molecular weight distribution index PDI of about 1-2.
In the film-forming hydrophobic monomer in the step (2), the mass ratio of the hard monomer to the soft monomer is 1:9-9: 1.
The invention synthesizes polymer-organic pigment hybrid latex through soap-free in-situ RAFT emulsion copolymerization. Synthesizing a chemical crosslinking type copolymer nano particle with the amphiphilic end active group particle size of 10-250nm by RAFT free radical polymerization induced self-assembly (PISA), and using the chemical crosslinking type copolymer nano particle to adsorb and disperse organic pigment particles. The chemical crosslinking type copolymer nano-particles are used for regulating and controlling the in-situ soap-free RAFT emulsion polymerization of film-forming hydrophobic monomers on the surface of the organic pigment and regulating and controlling the structure and the composition of a coating polymer, so that a series of polymer/organic pigment hybrid latex which is uniformly coated and stably dispersed is obtained.
Compared with the prior art, the invention has the following advantages:
the invention relates to a method for designing and synthesizing a chemical crosslinking type copolymer nano particle with amphiphilic end active group particle size of 10-250nm by taking water as a medium and inducing self-assembly (PISA) through RAFT free radical polymerization, and the chemical crosslinking type copolymer nano particle is used for coating organic pigment micro particles.
Secondly, the chemically crosslinked copolymer nanoparticles used in the research overcome the defects that the latex stability is lost and the physical property of the glue film is affected due to the fact that an emulsifier used in the conventional pigment encapsulation is easy to desorb and migrate, and are covalently stable on the surface of the pigment, so that the latex stability and the coating stability are improved.
Compared with other polymer/organic pigment hybrid latex, the polymer/organic pigment hybrid latex synthesized by soap-free in-situ RAFT (reversible addition-fragmentation chain transfer) emulsion copolymerization overcomes the defects of poor dispersion stability, uncontrollable molecular structure of a coating polymer and the like of the conventional hybrid latex.
The hybrid latex prepared by soap-free in-situ RAFT emulsion copolymerization has the characteristics of high dispersion stability, high pigment coating rate, clear and controllable structure of a coating polymer layer and the like, and is suitable for surface coating modification of various pigments.
Drawings
FIG. 1 is a schematic diagram of the process of synthesizing polymer-organic pigment hybrid latex by soap-free in-situ RAFT emulsion copolymerization.
Figure 2 is the emulsion particle size growth process during soap-free in situ RAFT emulsion copolymerization of example 9 of table 2. (size represents the size of particle diameter)
FIG. 3 is a transmission electron micrograph of an unmodified pigment and a prepared polymer-organic pigment hybrid latex, wherein FIG. 3a is a transmission electron micrograph of an unmodified pigment, and FIGS. 3b and 3c are transmission electron micrographs of a polymer-organic pigment hybrid latex prepared in example 9 of Table 2.
Detailed Description
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Examples
According to the feeding proportions and conditions shown in table 1 and table 2, a polymer/organic pigment hybrid latex was prepared by the following steps:
1. a series of chemical crosslinking type copolymer nano particles with amphiphilic end active group particle size of 10-250nm are synthesized by RAFT free radical polymerization induced self-assembly (PISA) and used for adsorbing and dispersing organic pigment particles. The specific experimental steps are as follows: synthesizing the PISA copolymer nano particles by adopting a sulfur-containing and sulfur-free RAFT free radical polymerization mode.
Taking examples 1-6 (conventional sulfur-containing RAFT polymerization) as an example, (1) a water-soluble macro-RAFT agent was first synthesized: in example 1, initiator ACVA (0.017g, 0.064mmol), small molecule RAFT reagent CDPA (0.26g, 0.64mmol), water soluble cationic monomer DMA (10g, 0.064mol) were added, THF10g was added and reaction was carried out at 66 ℃ for 12 h. CDPA to ACVA molar ratio of 10: 1, the molar ratio of DMA to CDPA is 100, synthesizing the product1The conversion rate obtained by HNMR test is 75%, and the polymerization degree is 75; in examples 2 and 3, the molar ratio of DMA to CDPA was 50, and the product was synthesized so as to1HNMR test gave a conversion of 74% and a degree of polymerization of 37. Adding DMA and PEO8MA, MMA (5.03g, 8.7g, 1.28g, 50:30:20mol: mol), CDPA (0.26g, 0.64mmol), ACVA (0.017g, 0.064mmol) were added to the solvent THF15g and reacted at 66 ℃ for 12 hours. The actual degree of polymerization is shown in the table. In examples 4-6, monomer is present in moles with CDPAThe ratios were 100, 50, respectively, and the actual polymerization degrees are shown in Table 1. The synthesized macromolecular RAFT reagent is purified by petroleum ether precipitation. (2) Secondly, chain extension self-assembly of insoluble blocks: and (2) adding the macromolecular RAFT reagent and BzMA synthesized in the step one into AIBN serving as an initiator, reacting for 10 hours at 70 ℃ by using an ethanol/water (85: 15 wt%) solvent, and performing RAFT dispersion polymerization to extend chain by using a monomer insoluble in a system to generate a polymer chain segment insoluble in a polymerization system. The ratio of macro RAFT agent to AIBN was 10: 1. PDMA-CDPA (1.71g, 0.00014mol), B were added as in example 1zMA (2.5g, 0.0142mol), AIBN (0.0047g, 0.0284mmol), solvent ethanol/water (20.278g/3.579g) was added. The molar ratio of PDMA-CDPA to AIBN was 5: 1. In examples 1, 2, 4 and 5, AIBN, BzMolar ratio of MA to macromolecular RAFT agent 100, in examples 3 and 6, BzThe molar ratio of MA to the macromolecular RAFT reagent is 350, the specific conversion rate reaches more than 99 percent, and the MA and the macromolecular RAFT reagent are self-assembled into the copolymer nano particle aggregate along with the growth of chain segments. (3) And (2) after the step (2), continuously adding a cross-linking agent EGDMA and an initiator into the solution, and reacting for 8 hours to realize the covalent stability of the self-assembled aggregate. EGDMA (0.28g, 0.0014mol) and AIBN (0.00047g, 0.00284mmol) were injected into the reaction mixture as in example 1. In examples 1, 2, 4 and 5, the molar ratio of EGDMA to macro RAFT reagent was 12, and the conversion was 84%, and in examples 3 and 6, the molar ratio of EGDMA to macro RAFT reagent was 25, and the conversion was 82%. Sulfur-containing PISA copolymer nanoparticles were synthesized therefrom.
In example 7-12 (sulfur-free RAFT polymerization), (1) a water-soluble macro-RAFT reagent was synthesized first, and a sulfur-free terminal ω -vinyl macro-RAFT reagent was synthesized in situ on the surface of pigment particles by catalytic chain transfer polymerization using a cobalt complex as a catalyst, and purified by petroleum ether precipitation. In examples 7 to 9, DMA (10g, 0.064mol), CoBF (2.5mg, 100ppm) and AIBN (0.105g, 0.64mmol) were added, and THF10g was added as a solvent. To be provided with1HNMR found an average degree of polymerization of 17, and in examples 10 to 12, DMA and PEO were added8MA, MMA (5.03g, 8.7g, 1.28g, 50:30:20mol: mol), CoBF (2.5mg, 100ppm), AIBN (0.105g, 0.64mmol) were added as a solvent THF16g and reacted at 66 ℃ for 12 hours. The actual degree of polymerization is shown in the table. (2) Secondly insoluble blocksChain extension self-assembly of segments: using AIBN as initiator, adding macromolecular RAFT reagent synthesized in the step one, using ethanol/water (85: 15 wt%) as solvent, BzInjecting MA at the speed of 0.6mL/h by adopting a starvation feeding mode, reacting for 4h at 70 ℃ after feeding is finished, and carrying out chain extension by using monomers insoluble in a system through RAFT dispersion polymerization to generate a polymer chain segment insoluble in a polymerization system. The ratio of macro RAFT agent to AIBN was 10: 1. PDMA (5g, 0.0019mol), B are added as in example 7zMA (3.35g, 0.019mol), AIBN (0.062g, 0.38mmol), solvent ethanol/water (35.5g/6.26g) was added. The molar ratio of PDMA-CDPA to AIBN was 5: 1. Examples 7 to 9, BzThe molar ratio of MA to the macro RAFT reagent is 10, 30 and 50 respectively, and the same applies to examples 10-12. Self-assemble into copolymer nanoparticle aggregates as the segments grow. (3) And 2, continuously injecting a mixed solution of a cross-linking agent EGDMA and an initiator into the solution at the speed of 0.6mL/h, reacting for 4h after the feeding is finished to achieve complete conversion, and adding the cross-linking agent EGDMA during the particle synthesis to realize the covalent stabilization of the self-assembled aggregate. EGDMA (1.88g, 0.0095mol) and AIBN (0.0062g, 0.038mmol) were injected into the reaction mixture as in example 7. The molar ratio of EGDMA to macro RAFT reagent was 5 in examples 7 and 10, and 10 in examples 8, 9, 11 and 12. Sulfur-free PISA copolymer nanoparticles were synthesized therefrom.
The series of copolymer nanoparticles are dispersed with pigments according to different mass concentration ratios in a water system, 20mL of water is added into a sample bottle, the pigment concentration is 5g/L, and the particle concentration is 1g/L-30g/L, so that the adsorption and dispersion rules of the copolymer nanoparticles in water for pigment particles are researched.
2. In-situ soap-free RAFT emulsion polymerization of a film-forming hydrophobic monomer on the surface of an organic pigment is regulated and controlled by the chemical crosslinking type copolymer nanoparticles, so that soap-free chemical crosslinking type copolymer nanoparticle-coated organic pigment hybrid latex is obtained. The specific experimental steps are as follows: a pigment dispersion having a solid content of 20% by weight was prepared in an optimum ratio of copolymer nanoparticle/pigment adsorption dispersion mass, and the obtained pigment dispersion was charged into a four-necked flask and purged with nitrogen gas for 30 minutes under stirring at 300 rpm. Subsequently, an acrylic monomer and an aqueous initiator solution previously subjected to oxygen-discharging treatment were added by injection (injection rate of 0.3 mL/min). For each addition, the volume of aqueous initiator solution added was equal to the volume of monomer. After the addition, the reaction was continued under the same conditions for 2-3 h. During the polymerization, a nitrogen atmosphere was maintained, and the polymerization temperature was 80 ℃.
Comparative example 1:
the macromolecule polymerized in the first step of the example RAFT reagent P (DMA)75CDPA was dissolved in water, pigment Red 170 was added and homogenized by ultrasound to obtain a pigment dispersion. And then directly adding the acrylic ester monomer subjected to oxygen-discharging treatment in advance and an aqueous solution of an initiator for polymerization to obtain the polymer/organic pigment hybrid latex.
TABLE 1
According to the feeding proportion and conditions shown in Table 1, a series of chemical crosslinking type copolymer nanoparticles with amphiphilic end active group particle size of 10-250nm are synthesized by RAFT free radical polymerization induced self-assembly (PISA) and are used for adsorbing and dispersing organic pigment particles. According to the difference of sulfur-containing and sulfur-free macromolecular RAFT reagents, insoluble block monomers and crosslinking monomers, the chemical crosslinking type copolymer nanoparticles with amphiphilic end active group with different structures and the particle size of 10-250nm can be obtained. Taking the example 1, the example 4, the example 7 and the example 10 as examples, the molecular structural formula of the chemically crosslinked copolymer nanoparticle with the amphiphilic end active group having the particle size of 10-250nm is as follows:
a. in b, x is 7; n is 75; m is 100; z is 10; a: b: c is 50:30:20(mol: mol); a + b + c ═ n ═ 75;
c. in d, x is 7; n is 17; m is 10; z is 5; a: b: c is 50:30:20(mol: mol); a + b + c is 16.
As can be seen from examples 1 to 12, when the nanoparticle/pigment adsorptive dispersion mass concentration ratio is (2.5 to 3.5):1, the pigment dispersion particle size is in a smaller range, facilitating the subsequent soap-free RAFT polymerization control test. Therefore, the ratio between the particles and the pigment in the subsequent examples is preferably (2.5-3.5): 1.
TABLE 2
The obtained polymer/organic pigment hybrid latex is used as ink for ink-jet printing and is applied to the ink-jet printing of cotton fabrics. The printed fabric was tested for its crockfastness, hand, air permeability, etc. and the results are shown in table 3.
The measurement method of each data is as follows:
1. the average particle size of the hybrid latex was obtained by measuring the particle size of the polymer/organic pigment hybrid latex using a Nano-laser particle sizer (Nano-90 type Nano-laser particle sizer (malvern instruments ltd, uk)).
2. The dry and wet rubbing fastness test refers to the standard GB/T3920-2008 ' color fastness to rubbing ' of textile color fastness test '. The sample was 50mm X200 mm, two each in warp and weft direction, and the standard rubbing cotton cloth was 50mm X50 mm.
3. Testing the hand feeling performance: the fabric after the closed-mesh touch finishing is graded by one person as a small group, and the printed fabric is graded in hand feeling according to different hand feelings, wherein the specific grading method is that the hand feeling is graded from two aspects of softness and smoothness, the grade is 5, the grade 1 is the worst, the fabric is hard in hand feeling, the smoothness is poor, the grade 5 is the best, and the fabric is soft and smooth in hand feeling.
TABLE 3
The schematic diagram of the soap-free in-situ RAFT emulsion copolymerization to form polymer-organic pigment hybrid latex described in the above examples is shown in fig. 1. Following the particle size growth of the emulsion during the soap-free in situ RAFT emulsion copolymerization of example 9, the particle size growth results are shown in figure 2, and it can be seen that the particle size of the emulsion increases with the progressive addition of monomer, which laterally demonstrates that the surface of the pigment is coated with a shell during polymerization. The coating of the polymer is further verified by a transmission electron microscope, fig. 3a and fig. 3b are TEM images of pigment red 170 original pigment and polymer-organic pigment hybrid latex, respectively, and it can be seen from the TEM images that the surface of the polymer-organic pigment hybrid latex prepared by soap-free in-situ RAFT emulsion polymerization is coated with a thick shell, and the pigment is well dispersed.
As can be seen from Table 3, the polymer/organic pigment hybrid latex synthesized by the soap-free in-situ RAFT emulsion copolymerization method can effectively improve the existing pigment printing technology, the dry and wet rubbing fastness is 4-5 grade, and the printed fabric has soft hand feeling. The particle size of the hybrid latex is 200-250nm, and the hybrid latex can reduce the blockage of a nozzle when being used as ink for ink-jet printing.
Claims (10)
1. A preparation method of soap-free chemical crosslinking type copolymer nanoparticle-coated organic pigment hybrid latex is characterized by comprising the following steps:
(1) synthesizing a chemical crosslinking type copolymer nano particle with the particle size of amphiphilic end active group of 10-250nm by RAFT free radical polymerization induction self-assembly;
(2) mixing the chemically crosslinked copolymer nanoparticles with a pigment in a water system to generate a pigment dispersion liquid, wherein the chemically crosslinked copolymer nanoparticles are used for regulating and controlling the in-situ soap-free RAFT emulsion polymerization of a film-forming hydrophobic monomer on the surface of an organic pigment to obtain the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex.
2. The method for preparing the organic pigment hybrid latex coated with the soap-free chemically crosslinked copolymer nanoparticles according to claim 1, wherein the step (1) of synthesizing the chemically crosslinked copolymer nanoparticles specifically comprises:
(1.1) Synthesis of Water-soluble macromolecular RAFT reagent:
the preparation method comprises the steps of taking ACVA as an initiator, adding a small molecular RAFT reagent and a water-soluble monomer, synthesizing the water-soluble macromolecular RAFT reagent through RAFT solution polymerization, carrying out sulfur-free RAFT polymerization by taking a cobalt complex as a catalyst, adopting a catalytic chain transfer polymerization method to synthesize the sulfur-free end omega-vinyl macromolecular RAFT reagent on the surface of pigment particles in situ, and carrying out petroleum ether precipitation purification.
(1.2) chain extension self-assembly of insoluble blocks: AIBN is used as an initiator, hydrophobic monomers are subjected to chain extension through RAFT dispersion polymerization to generate a high molecular chain segment which is insoluble in a polymerization system, the high molecular chain segment is self-assembled into a copolymer nanoparticle aggregate along with the growth of the chain segment, and a cross-linking agent is added during the particle synthesis to realize the covalent stability of the self-assembled aggregate, so that the chemical cross-linking type copolymer nanoparticle is obtained.
3. The method for preparing the soap-free chemically cross-linked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (1.1), the small molecule RAFT reagent is 4-cyano-4- (dodecylsulfonylthiocarbonyl) sulfonylvaleric acid, 4-cyano-4- (propylsulfonylthiocarbonyl) sulfonylvaleric acid or α -dithionaphthoic acid isobutyronitrile ester;
the cobalt complex is one or more of dihydrate bis (boron difluoride benzodioxole oxime) cobalt and dihydrate bis (boron difluoride benzodioxole oxime) cobalt.
4. The method for preparing the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (1.1), the water-soluble macro-molecule RAFT reagent is PDMA or PEOx+1One or more of MA, PMAA and PGMA, the target polymerization degree is 10-100, and the molecular weight is 2000-70000.
5. The method for preparing the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex as claimed in claim 1, wherein in the step (1.2), the hydrophobic monomer is one or more of BzMA, MEA, HPMA and BA, the target degree of polymerization is 10-350, and the molecular weight is 2000-160000.
6. The method for preparing the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (1.2), the crosslinking monomer is one or two of ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate, the target degree of polymerization is 5-50, and the molecular weight is 1000-24000.
7. The preparation method of the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (2), the pigment is pigment red 170, titanium dioxide pigment, phthalocyanine blue pigment or benzidine yellow pigment.
8. The method for preparing the soap-free chemically cross-linked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (2), the film-forming hydrophobic monomer is a combination of a hard monomer and a soft monomer, the hard monomer is methyl methacrylate, isobutyl methacrylate or benzyl methacrylate, and the soft monomer is butyl methacrylate or butyl acrylate.
9. The method for preparing the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 8, wherein in the step (2), the mass ratio of the hard monomer to the soft monomer in the film-forming hydrophobic monomer is 1:9-9: 1.
10. The method for preparing the soap-free chemically crosslinked copolymer nanoparticle-coated organic pigment hybrid latex according to claim 1, wherein in the step (2), the film-forming hydrophobic monomer is injected, and the polymerization feeding rate is 0.1-10 mL/min.
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