CN103936941A - Amphiphilic core-shell emulsion adhesive for pigment printing of textile and preparation method thereof - Google Patents
Amphiphilic core-shell emulsion adhesive for pigment printing of textile and preparation method thereof Download PDFInfo
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Abstract
The invention provides an amphiphilic core-shell emulsion adhesive for pigment printing of textile and a preparation method thereof, and belongs to the field of printing and dyeing. The amphiphilic core-shell emulsion adhesive is of a core-shell structure, wherein the core layer is a soft monomer-based acrylate copolymer containing a crosslinking monomer; the shell layer is a hard monomer-based segmented copolymer comprising an acrylate chain section and an acrylamide chain section. The preparation method comprises the following steps: (1) adding some monomers, initiators, emulsifying agents and the like to a first bottle, and copolymerizing through common free radicals to obtain the core layer; (2) pumping the product into a second bottle, adding the rest hydrophobic monomer, emulsifying agents, initiators, a catalyst and a ligand, and carrying out reverse atom transfer radical polymerization to obtain a hydrophobic core-shell copolymer; (3) adding all hydrophilic monomers and the rest initiators to the second bottle, and continuously carrying out reverse atom transfer radical polymerization to obtain an amphiphilic core-shell copolymer of which the shell layer contains a hydrophilic chain section. The amphiphilic core-shell emulsion adhesive can be used as an adhesive for pigment printing, and has the effects of decreasing the dosage and reducing mesh clogging and roller adhering.
Description
Technical field
The invention belongs to Polymer Synthesizing and printing technology field.Specifically a kind of amphiphilic core-shell emulsion tackiness agent for textile coating stamp and preparation method thereof.
Background of invention
China has become textile printing and dyeing big country.China's tprinted Fabrics output has exceeded 15,000,000,000 meters in 2010, in recent years declines to some extent, and 2013 annual production are 13,500,000,000 meters.But the raising of throughput and economic benefit can not synchronized development.Compared with world level, China's dyeing and printing products still concentrates on low and middle-grade, and added value of product is lower.At present, the production of tprinted Fabrics mainly contains dye printing and two kinds of techniques of pigment printing.Compared with dye printing, pigment printing has the advantages such as power consumption is low, water consumption is few, quantity of wastewater effluent is few, is widely used.Pigment printing technical development is very fast, and the whole world has 55% PRINTED FABRIC to be completed by pigment printing according to statistics, and in the U.S., pigment printing fabric accounts for 80% of PRINTED FABRIC total amount; In China, this ratio is about 35% (also report and reached 60%).For example, 2013 annual production are 13,500,000,000 meters of tprinted Fabricss, wherein nearly 5,000,000,000 meters of pigment printing cloth (calculating by 35%), and conservative estimation tprinted Fabrics will reach 160,000 tons to the demand of tackiness agent, and the market requirement is huge.Existing pigment printing binding agent also exists some problems to need to improve, for example, the contradiction of printing fastness and feel, must be taking the crosslinked film forming of tackiness agent as prerequisite because obtain enough fastness, but crosslinked film forming makes the feel variation of printed fabrics, therefore will improve feel and must sacrifice fastness; In addition, also have the problem of stamp network blocking, if the breakdown of emulsion film forming of adhesive agent emulsion occurs in the course of processing, produce serious network blocking or roll banding.
Therefore, the synthesis technique of tackiness agent and new product development are the domestic and international Research Emphasis in pigment printing binding agent field, and the tackiness agent kind of exploitation cannot win number up to now.The conventional tackiness agent of domestic industry circle mainly contains three major types at present: acrylic binder, divinyl tackiness agent and polyurethane binder, wherein acrylic binder uses the most general.Although pigment printing binding agent preparation technology is ripe, but still require further improvement the performance of tackiness agent at the aspect such as colour fastness and the network blocking roll banding of feel contradiction and pigment printing technique that solves pigment printing fabric.
Utilize controllable free-radical letex polymerization synthetic obtain the controlled amphiphilic block copolymer of structure be in recent years since the study hotspot in Polymer Synthesizing field.Controllable free-radical polymerisation and free radical core-shell emulsion polymerization technology combine for the synthesis of amphiphilic core-shell emulsion tackiness agent, are conducive to improve the avidity of tackiness agent and fabric and reduce binder dosage, thereby improve fabric feeling and do not sacrifice fabric fastness.Meanwhile, amphiphilic the stable of emulsion that be conducive to of polymkeric substance, can reduce the irregular breakdown of emulsion of emulsion and then reduce network blocking odds in stamp process.
Summary of the invention
The object of the invention is to provide a kind of amphiphilic core-shell emulsion tackiness agent and synthetic method thereof for textile coating stamp.
One of the problem to be solved in the present invention is to provide a kind of novel pigment printing binding agent, and this tackiness agent has nucleocapsid structure, and shell polymkeric substance has parents' character.
Two of the problem to be solved in the present invention is to provide a kind of novel polymerization technique, and this technology is applied in the middle of core-shell emulsion polymerization.Specifically be to select a kind of controllable free-radical polymerisation technology, be combined utilization with common radical polymerization technique, preparation has the emulsion of the nucleocapsid structure of parents' character.Selected controllable free-radical polymerisation technology is reverse atom transfer radical polymerization technology more specifically.
The invention provides a kind of amphiphilic core-shell emulsion tackiness agent for textile coating stamp, is a kind of nucleocapsid structure water miscible liquid, and emulsion particle is made up of stratum nucleare and shell two portions.Described stratum nucleare is the acrylate copolymer of soft monomer, hard monomer and cross-linking monomer; Described shell is the acrylate copolymer segment of hard monomer, soft monomer and function monomer and the segmented copolymer of hydrophilic segment composition.Soft monomer described in reactant formula is one or more the combination in butyl acrylate, ethyl propenoate or 2-EHA; Described hard monomer is one or both in methyl methacrylate, vinylbenzene or vinyl cyanide; Described cross-linking monomer is one or both the combination in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, the own ester of vinylformic acid hydroxyl, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410; Described hydrophilic monomer is acrylamide; Described function monomer is one or both in acrylic or methacrylic acid; Described initiator is ammonium persulphate or Potassium Persulphate; Described catalyzer is cupric bromide or cupric chloride; Described part is pentamethyl-diethylenetriamine, bipyridine, 4,4 '-bis--n-heptyl-2, the one in 2 '-dipyridyl, 4,4 '-bis-(5-nonyl)-2,2 '-dipyridyl; Described emulsifying agent is the combination of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, octylphenol polyethylene glycol ether.Described alkali is the one in sodium bicarbonate, sodium carbonate, sodium hydroxide.
The invention provides a kind of preparation method of amphiphilic core-shell emulsion tackiness agent.The preparation method of amphiphilic core-shell emulsion tackiness agent is divided into a three stage polymerization, carries out respectively in No. 1 and No. 2 two polymerization bottles, comprises the following steps:
I section polymerization: in No. 1 polymerization bottle, add the composition such as soft monomer and hard monomer and suitable cross-linking monomer, initiator and emulsifying agent of part, utilize free radical emulsion copolymerization to make stratum nucleare multipolymer;
II section polymerization: I section gained stratum nucleare multipolymer is delivered to polymerization bottle No. 2 by pipeline, and adding initiator, the catalyzer of remaining soft monomer, hard monomer, emulsifying agent and reverse atom transfer radical polymerization, reaction certain hour obtains the core-shell copolymerized thing (macromole evocating agent) containing initiator;
III section polymerization: after above-mentioned two sections of polymerizations complete, add all hydrophilic monomers, remaining initiator and other auxiliary agents, the polymer chain end that contains initiator on shell surface further carries out reverse atom transfer radical polymerization, and reaction certain hour obtains the amphiphilic core-shell copolymerized thing of shell containing hydrophilic segment.
The emulsion particle structure of gained of the present invention as shown in Figure 1.Emulsion particle is hud typed.The main component of its core is taking butyl acrylate as main, and other acrylic ester monomers are auxiliary multipolymer, as shown in Figure 1A.The main component of shell is the segmented copolymer of polyacrylic ester and polyacrylamide, has parents' character, and as shown in Figure 1B and C, hydrophobic chain segment is wherein mainly polyacrylic ester, shown in Figure 1B short chain; In addition, the hydrophilic segment taking polyacrylamide as main component is present in the outermost layer of shell, directly contacts, with water medium as shown in Fig. 1 C long-chain.Molecule segment shown in Figure 1B and 1C forms the shell of emulsion particle jointly, forms Structure of Core/shell Emulsion particle together with wrapped A part.Prepared by the present invention has the isostructural segmented copolymer of polyacrylamide-polyacrylic ester, wherein polyacrylic ester section being because have long hydrocarbon hydrophobic chain and contain a considerable amount of ester bonds, and can set up strong hydrophobic binding containing between the coating of hydrophobicity organic group; And polyacrylamide section wherein contains a large amount of polarity hydrophilic radicals, can, with the polar group of fiber surface as-COOH forms hydrogen bond, therefore by parents' effect of multipolymer, coating particle be fixed on to fiber surface, there is higher colour fastness.Amphiphilic due to multipolymer can obtain good color fastness under the thinner condition of binder film, therefore adopts amphiphilic block copolymer can reduce the consumption of tackiness agent, obtains good feel.
The invention discloses a kind of preparation method who makes amphiphilic core-shell structure binder, this tackiness agent is for the pigment printing of textiles.Key of the present invention is that adopted reverse atom transfer radical polymerization technology can introduce hydrophilic segment the shell polymkeric substance of tackiness agent, therefore can improve wetting ability and the dispersiveness of adhesive agent emulsion particle, see and improve colour fastness to greatest extent and do not affect feel.And emulsion particle is made to nucleocapsid structure, increase the stability of emulsion to shearing action.Can well avoid the in advance demulsifying phenomenon of emulsion in the course of processing, eliminate or improve network blocking, the roll banding problem in dyeing and printing process.
1, about the selection of adhesive reaction thing component
In pigment printing binding agent of the present invention, adhesive reaction thing component comprises various monomers, emulsifying agent and initiator.In monomer, comprise again low Tg soft monomer, high glass transition temperature hard monomer and there is the functional monomer of crosslinking kinetic energy based group, the cross-linking monomer that the present invention selects is not all containing the function monomer of reaction process release formaldehyde.The composition of each composition is as follows, and unit is mass parts:
Soft monomer described in reactant formula is one or more the combination in butyl acrylate, ethyl propenoate or 2-EHA; Described hard monomer is a kind of in methyl methacrylate, vinylbenzene or vinyl cyanide or two kinds; Described cross-linking monomer is one or both the combination in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, the own ester of vinylformic acid hydroxyl, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410; Described hydrophilic monomer is acrylamide; Described function monomer is one or both in acrylic or methacrylic acid; Described initiator is ammonium persulphate or Potassium Persulphate; Described catalyzer is cupric bromide or cupric chloride; Described part is pentamethyl-diethylenetriamine, bipyridine, 4,4 '-bis--n-heptyl-2, the one in 2 '-dipyridyl, 4,4 '-bis-(5-nonyl)-2,2 '-dipyridyl; Described emulsifying agent is the combination of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, octylphenol polyethylene glycol ether.Described alkali is the one in sodium bicarbonate, sodium carbonate, sodium hydroxide.
2, about the preparation method of tackiness agent.
According to technical scheme provided by the invention, the preparation method of described amphiphilic core-shell emulsion tackiness agent, feature is that formula rate is counted by weight, comprises the following steps:
(1) under high pure nitrogen or argon shield, soft monomer, hard monomer and the functional monomer of 1/8～1/3 in above-mentioned reactant formula, whole cross-linking monomer, 1/8～1/3 initiator and 2/3～3/4 emulsifying agent and deionized water are added to reaction flask No. 1, at 20 DEG C～50 DEG C, stir pre-emulsification 15min～30min, be warming up to 75 DEG C～90 DEG C; After initiated polymerization, be incubated 1～3 hour, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/4～2/3 initiator and remaining emulsifying agent to No. 2 bottles, add alkali, catalyzer, part, be warming up to 60 DEG C～80 DEG C; drip remaining soft monomer, hard monomer and function monomer, dropwise rear insulation 1.5～4 hours.Be cooled to after completion of the reaction 30～50 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole hydrophilic monomers and remaining initiator, be warming up to 60 DEG C～80 DEG C, react 1～3 hour.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
The properties of the product of the present invention making by aforesaid method adopts following method to detect.
Emulsion solid content is measured
Weighing bottle is dried to constant weight at 100 DEG C～105 DEG C, the sample (m1) of accurate weighing 2g left and right is in weighing bottle, being placed in 100 DEG C～105 DEG C Constant Temp. Ovens dries to constant weight, then be transferred in moisture eliminator and after cooling 30min, accurately weigh (m2), solid content can be calculated as follows:
Solid content (%)=m2/m1 × 100%
Emulsion viscosity is measured
Adopt the viscosity of the DV-III ULTRA type rotary viscosity design determining adhesive agent emulsion of Brookfield company of the U.S..
Adhesive agent emulsion particle transmission electron microscope observation
Adopt NEC company to manufacture JEM-1200EX type transmission electron microscope, under 10,000～300,000 magnification, observe emulsion particle structure.
Emulsion particle diameter and particle size distribution measuring
Adopt particle diameter and the size distribution of Nano-ZS90 type Zeta potential and the particle size analyzer mensuration adhesive agent emulsion of Malvern instrument company of Britain.
Stability of emulsion is measured
Adopting 80-1 type whizzer is by centrifugal sample 30min under 4000rpm at rotating speed.Get the adhesive agent emulsion of 1ml after centrifugal with transfer pipet again, after dilution, use 722 grating spectrophotometers, the absorbance A 30 of mensuration diluent; Use the same method and measure the not absorbance A 0 of centrifugal sample.The ratio of the absorbancy before the absorbancy after emulsion is centrifugal and centrifugal treating is referred to as than absorbancy R30, the index of centrifugal settling stability as weighing emulsion:
The amphiphilic test of emulsion
Adopt emulsion to measure the avidity of emulsion to fabric in the film forming adsorptive capacity of surface of cotton fabric.Take a certain amount of copolymer emulsion, and be diluted to certain multiple.At 40 DEG C, 60 DEG C and 80 DEG C, cotton fabric is immersed to emulsion respectively, reach after equilibrium adsorption, by the absorbancy of the remaining system of spectrophotometric determination, calculate absorbance ratio, and then try to achieve the copolymer quality adsorbing on fabric.The main absorption property of measuring the copolymer emulsion that contains different close hydrophobic segment ratios.
Adopt the pigment avidity of the dispersion stabilization characterize polymers of pigment under the effect of copolymer emulsion.Get the pigment of certain mass, the segmented copolymer emulsion that joins different amounts stirs certain hour, wait to leave standstill for some time observe system state, then pigments system is put into supersonic cleaning machine supersound process 30nin, after stable system, particle diameter and size-grade distribution and the stability of test pigments system.
Tackiness agent is for the colour fastness test of pigment printing
The tackiness agent of synthesized is modulated to mill base according to conventional formula together with other composition, then cotton or wash/cotton (80/20) fabric are carried out manual table printing, test the brushing fastness of PRINTED FABRIC after stamp according to GB/T420-1990; According to the crock fastness of GB/T3920-1997 test PRINTED FABRIC; According to the colour fastness to washing of GB/T3921.3-1997 test fabric.
The test of tackiness agent feel
The tackiness agent of synthesized of the present invention is modulated to mill base according to conventional formulation together with other composition, then cotton or wash/cotton (80/20) fabric are carried out to manual table printing, the feel of the fabric that the comparison of employing hand palpating manipulation is printed.
The test of tackiness agent formaldehyde
First by the tackiness agent of synthesized of the present invention by following art breading fabric: adopt tackiness agent 300g/L bis-to soak two and roll pure cotton fabric, then dry being greater than at 100 DEG C, finally bake 2min 150 DEG C of left and right.According to contained formaldehyde in GB/T2912.1-1998 test fabric.
Advantage of the present invention is:
(1) the present invention adopts the shell of amphiphilic diblock copolymer as Structure of Core/shell Emulsion.Avidity to fabric is provided in tackiness agent film forming, with respect to common hydrophobicity Structure of Core/shell Emulsion, is adsorbed in more securely fabric face.Simultaneously hydrophobic stratum nucleare has been fixed pigment particles, therefore can be few with tackiness agent, under the thinner prerequisite of film forming, obtain higher color fastness.Solve preferably the contradictory problems of pigment printing feel and colour fastness.
(2) the present invention adopts the shell of amphiphilic diblock copolymer as Structure of Core/shell Emulsion.In the forming process of adhesive agent emulsion, amphiphilic copolymer provides self-emulsifying action, improves the stability of emulsion, and can regulate by the content of amphiphilic copolymer and proportioning the stability of emulsion.Network blocking in pigment printing technological process and the problem of roll banding are solved preferably.
(3) the present invention adopts stratum nucleare emulsion cooling and adopt acrylic ester monomer that end the contains hydroxyl method as cross-linking monomer, the acrylic ester emulsion particle that contains terminal hydroxy group is made hud typed, and wherein most of soft monomer is at stratum nucleare; Most hard monomer is at shell.Therefore, the present invention improves the stability of adhesive agent emulsion to shearing action in improving polymer adhesive fastness, can effectively avoid or reduce network blocking, roll banding problem in the coating dye printing course of processing.
(4) the present invention adopts terminal hydroxy group acrylate, and all cross-linking monomers do not contain the compositions such as n-methylolacrylamide, and release formaldehyde not completely, is outstanding environmentfriendly products.
Brief description of the drawings
Accompanying drawing 1 emulsion particle structural representation.A, stratum nucleare; B, hydrophobicity shell; C, wetting ability shell
Embodiment
Further illustrate feature of the present invention with specific embodiment below.
Embodiment 1
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, 2-EHA, methyl methacrylate, vinylbenzene, vinylformic acid and the methacrylic acid of 1/8 in above-mentioned reactant formula, whole Hydroxyethyl acrylate, 1/8 ammonium persulphate, 2/3 sodium lauryl sulphate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 20 DEG C, stir pre-emulsification 30min, be warming up to 75 DEG C; After initiated polymerization, be incubated 3 hours, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/4 ammonium persulphate, sodium lauryl sulphate and octylphenol polyethylene glycol ether to No. 2 bottles; add sodium bicarbonate, cupric bromide, pentamethyl-diethylenetriamine; be warming up to 60 DEG C; drip remaining 2-EHA, methyl methacrylate, vinylbenzene, vinylformic acid and methacrylic acid, dropwise rear insulation 4 hours.Be cooled to after completion of the reaction 30 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining ammonium persulphate, be warming up to 60 DEG C, react 3 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 2
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, 2-EHA, methyl methacrylate, vinyl cyanide and the vinylformic acid of 1/4 in above-mentioned reactant formula, whole Hydroxyethyl acrylate, 1/4 Potassium Persulphate, 3/4 Sodium dodecylbenzene sulfonate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 40 DEG C, stir pre-emulsification 15min, be warming up to 80 DEG C; After initiated polymerization, be incubated 2 hours, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/3 Potassium Persulphate, Sodium dodecylbenzene sulfonate and octylphenol polyethylene glycol ether to No. 2 bottles; add sodium carbonate, cupric chloride, bipyridine; be warming up to 70 DEG C; drip remaining 2-EHA, methyl methacrylate, vinyl cyanide and vinylformic acid, dropwise rear insulation 4 hours.Be cooled to after completion of the reaction 30 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining Potassium Persulphate, be warming up to 70 DEG C, react 2 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 3
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, butyl acrylate, methyl methacrylate, vinyl cyanide and the methacrylic acid of 1/4 in above-mentioned reactant formula, whole vinylformic acid hydroxy butyl ester, 1/4 ammonium persulphate, 3/4 Sodium dodecylbenzene sulfonate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 40 DEG C, stir pre-emulsification 20min, be warming up to 80 DEG C; After initiated polymerization, be incubated 2 hours, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/4 ammonium persulphate, Sodium dodecylbenzene sulfonate and octylphenol polyethylene glycol ether to No. 2 bottles; add sodium carbonate, cupric chloride, bipyridine; be warming up to 70 DEG C; drip remaining butyl acrylate, methyl methacrylate, vinyl cyanide and methacrylic acid, dropwise rear insulation 3 hours.Be cooled to after completion of the reaction 40 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining ammonium persulphate, be warming up to 70 DEG C, react 2 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 4
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, butyl acrylate, methyl methacrylate, vinylbenzene and the methacrylic acid of 1/4 in above-mentioned reactant formula, whole vinylformic acid hydroxy butyl ester, 1/4 Potassium Persulphate, 3/4 sodium lauryl sulphate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 40 DEG C, stir pre-emulsification 20min, be warming up to 80 DEG C; After initiated polymerization, be incubated 2 hours, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/4 Potassium Persulphate, sodium lauryl sulphate and octylphenol polyethylene glycol ether to No. 2 bottles; add sodium carbonate, cupric bromide, 4; 4 '-bis--n-heptyl-2; 2 '-dipyridyl; be warming up to 70 DEG C, drip remaining butyl acrylate, methyl methacrylate, vinylbenzene and methacrylic acid, dropwise rear insulation 3 hours.Be cooled to after completion of the reaction 40 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining Potassium Persulphate, be warming up to 70 DEG C, react 2 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 5
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, butyl acrylate, methyl methacrylate, vinyl cyanide and the vinylformic acid of 1/3 in above-mentioned reactant formula, whole vinylformic acid hydroxy butyl ester, 1/3 ammonium persulphate, 3/4 sodium lauryl sulphate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 50 DEG C, stir pre-emulsification 15min, be warming up to 90 DEG C; After initiated polymerization, be incubated 1 hour, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/3 ammonium persulphate, remaining sodium lauryl sulphate and octylphenol polyethylene glycol ether to No. 2 bottles; add whole sodium hydroxide, cupric chloride, 4; 4 '-bis-(5-nonyls)-2; 2 '-dipyridyl; be warming up to 80 DEG C, drip remaining butyl acrylate, methyl methacrylate, vinyl cyanide and vinylformic acid, dropwise rear insulation 1.5 hours.Be cooled to after completion of the reaction 50 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining ammonium persulphate, be warming up to 80 DEG C, react 1.5 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 6
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, ethyl propenoate, methyl methacrylate, vinylbenzene and the vinylformic acid of 1/3 in above-mentioned reactant formula, whole Hydroxyethyl acrylate, 1/3 ammonium persulphate, 3/4 sodium lauryl sulphate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 50 DEG C, stir pre-emulsification 15min, be warming up to 90 DEG C; After initiated polymerization, be incubated 1 hour, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/3 ammonium persulphate, remaining sodium lauryl sulphate and octylphenol polyethylene glycol ether to No. 2 bottles; add whole sodium carbonate, cupric chloride, bipyridine; be warming up to 80 DEG C; drip remaining ethyl propenoate, methyl methacrylate, vinylbenzene and vinylformic acid, dropwise rear insulation 1.5 hours.Be cooled to after completion of the reaction 50 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining ammonium persulphate, be warming up to 80 DEG C, react 1.5 hours.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Embodiment 7
Adhesive agent emulsion polymerization formula, each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
(1) under high pure nitrogen or argon shield, ethyl propenoate, methyl methacrylate, vinylbenzene and the methacrylic acid of 1/3 in above-mentioned reactant formula, whole Hydroxyethyl acrylate, 1/3 Potassium Persulphate, 1/2 sodium lauryl sulphate and octylphenol polyethylene glycol ether and whole deionized waters are added to reaction flask No. 1, at 50 DEG C, stir pre-emulsification 15min, be warming up to 90 DEG C; After initiated polymerization, be incubated 1 hour, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 2/3 Potassium Persulphate, remaining sodium lauryl sulphate and octylphenol polyethylene glycol ether to No. 2 bottles; add whole sodium carbonate, cupric chloride, bipyridine; be warming up to 80 DEG C; drip remaining ethyl propenoate, methyl methacrylate, vinylbenzene and methacrylic acid, dropwise rear insulation 1.5 hours.Be cooled to after completion of the reaction 50 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole acrylamides and remaining Potassium Persulphate, be warming up to 80 DEG C, react 1 hour.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
Pigment printing experiment and detection
Adopt serial parents' core-shell type paint printing adhesive of the present invention (SQHK series) to carry out pigment printing test to fabric, printing paste formula following (unit: g):
C.I. Pigment Yellow 73 31 10
Tackiness agent of the present invention (solid content approximately 35%) 20
Printing technology adopts the ordinary method of the manual table printing in laboratory, and the fabric color fastness after stamp and formaldehyde content test result are as shown in table 1.Table 1SQHK-1 coating series printing adhesive detects data
Claims (4)
1. for an amphiphilic core-shell emulsion tackiness agent for textile coating stamp, it is characterized in that, this tackiness agent is a kind of nucleocapsid structure water miscible liquid, and emulsion particle is made up of stratum nucleare and shell two portions.Described stratum nucleare is the acrylate copolymer of soft monomer, hard monomer and cross-linking monomer; Described shell is the segmented copolymer of hydrophobic chain segment and hydrophilic segment composition.The acrylate copolymer segment that described hydrophobic chain segment is made up of hard monomer, soft monomer and function monomer; Described hydrophilic segment is acrylamide polymer segment.
(1) described soft monomer is one or more the combination in butyl acrylate, ethyl propenoate or 2-EHA;
(2) described hard monomer is one or both in methyl methacrylate, vinylbenzene or vinyl cyanide;
(3) described cross-linking monomer is one or both the combination in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, the own ester of vinylformic acid hydroxyl, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410;
(4) described hydrophilic monomer is acrylamide;
(5) described function monomer is one or both in acrylic or methacrylic acid;
(6) described initiator is ammonium persulphate or Potassium Persulphate;
(7) described catalyzer is cupric bromide or cupric chloride;
(8) described part is pentamethyl-diethylenetriamine, bipyridine, 4,4 '-bis--n-heptyl-2, the one in 2 '-dipyridyl, 4,4 '-bis-(5-nonyl)-2,2 '-dipyridyl;
(9) described emulsifying agent is the combination of anion surfactant and nonionogenic tenside, and wherein anion surfactant is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate, and nonionogenic tenside is octylphenol polyethylene glycol ether;
(10) described alkali is the one in sodium bicarbonate, sodium carbonate, sodium hydroxide.
2. an amphiphilic core-shell emulsion tackiness agent as claimed in claim 1, it is characterized in that, this printing adhesive emulsion particle is amphiphatic hud typed structure, this hud typed structure comprises the shell and the stratum nucleare that is positioned at shell of outside, and the total amount of the composition that described stratum nucleare and shell contain is jointly: soft monomer 40～80; Hard monomer 10～20; Cross-linking monomer 5～10; Hydrophilic monomer 10～20; Function monomer 1～10; Initiator 0.2～0.5; Catalyzer 0.5～2; Ligand 1～4; Emulsifying agent 2～5; Alkali 0.05～0.5.Unit is mass parts.
3. a preparation method for amphiphilic core-shell emulsion pigment printing binding agent as claimed in claim 1, is characterized in that, comprises the following steps, and the unit of described ratio is mass parts:
(1) under high pure nitrogen or argon shield, soft monomer, hard monomer and the functional monomer of 1/8～1/3 in above-mentioned reactant formula, whole cross-linking monomer, 1/8～1/3 initiator and 2/3～3/4 emulsifying agent and deionized water are added to reaction flask No. 1, at 20 DEG C～50 DEG C, stir pre-emulsification 15min～30min, be warming up to 75 DEG C～90 DEG C; After initiated polymerization, be incubated 1～3 hour, afterwards naturally cooling, cooling.Under high pure nitrogen or argon shield, be transferred to reaction flask No. 2.
(2) under high pure nitrogen or argon shield; add 1/4～2/3 initiator and remaining emulsifying agent to No. 2 bottles, add alkali, catalyzer, part, be warming up to 60 DEG C～80 DEG C; drip remaining soft monomer, hard monomer and function monomer, dropwise rear insulation 1.5～4 hours.Be cooled to after completion of the reaction 30～50 DEG C.
(3) under high pure nitrogen or argon shield, in No. 2 bottles, add whole hydrophilic monomers and remaining initiator, be warming up to 60 DEG C～80 DEG C, react 1～3 hour.Be down to after completion of the reaction room temperature.Discharging obtains adhesive agent emulsion.
4. an amphiphilic core-shell emulsion tackiness agent as claimed in claim 1, is characterized in that, for the pigment printing of textiles.
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| CN115613375A (en) * | 2022-10-31 | 2023-01-17 | 广州市盛勤实业有限公司 | Paint printing process for synthetic fiber and blended fabric |
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