CN104119483A - Preparing method of modified acrylate emulsion - Google Patents
Preparing method of modified acrylate emulsion Download PDFInfo
- Publication number
- CN104119483A CN104119483A CN201410331416.1A CN201410331416A CN104119483A CN 104119483 A CN104119483 A CN 104119483A CN 201410331416 A CN201410331416 A CN 201410331416A CN 104119483 A CN104119483 A CN 104119483A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- acrylate
- preparation
- monomer
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A preparing method of a modified acrylate emulsion is disclosed. The modified acrylate emulsion is prepared by subjecting acrylate, methacrylate, vinyl acetate, acrylonitrile, acrylic acid, an organosilicone modified monomer, a crosslinking monomer, a surface active monomer, and the like to emulsion polymerization. The organosilicone modified monomer is linear organopolysiloxane containing alkenyl bonding to silicon. Polymerization is performed after the surface active monomer, the acrylate and/or the methacrylate are adopted to prepare a seed emulsion, thus reducing the using amount of an emulsifying agent, making polymerization stable and making the gel rate low.
Description
Technical field
The present invention relates to a kind of emulsion polymerisation process, especially a kind of preparation method of modified acrylate emulsion.
Background technology
Pigment printing refers to and utilizes tackiness agent, by water insoluble, do not have affinity and reactive pigment to anchor on fabric to fabric fibre, after drying and forming-film, realize the painted printing method with forming different patterns.Pigment printing is low with the simple cost of technique, only needs dry fixation and without washing, save water, electricity, gas after printing, and waste water is few, and becomes the main method of various fabrics (as sheet, singlet, bunting etc.) printing pattern.
Acrylic emulsion is as stamp emulsion binding agent, have advantages of that, the transparency strong to the adhesivity of pigment, fiber, good weatherability, film forming properties are good, but after acrylate film forming, ubiquity poor water resistance, the low temperature high temperature that becomes fragile becomes and sticks and stamp crock fastness is not good, feel is coarse shortcoming.And in swimming suit printing technology, because swimming suit in use needs to stand the long period of soaking of water, printing fastness, water tolerance, resistance to bond are had higher requirements, swimming suit adopts elastomeric special fabric to make simultaneously, require to there is good rebound performance after stamp emulsion film forming, but acrylate printing emulsion of the prior art is difficult to meet the demands.
Simultaneously, the preparation of existing ACRYLIC EMULSION adopts semi-continuous emulsion polymerization conventionally, comprise bottoming-intensification initiation-dropping-insulation-post-treating and other steps, first by water, after emulsifying agent and part mix monomer and initiator hybrid reaction certain hour, drip residue initiator and mix monomer, continue to react to polymerization and finish, it is steady that the method has polymerization, product homogeneous, particle diameter is little, the advantage such as flexibly simple to operate, but work as in vinylformic acid synthetic system in order to improve the stability of emulsion, water tolerance after film forming etc. and adding when reactive emulsifier, in participation polymerization process, easily there is autohemagglutination in reactive emulsifier, cannot give full play to emulsifying property.
Summary of the invention
The problem existing in order to solve above-mentioned prior art, the invention provides a kind of preparation method of modified acrylate emulsion, the method is carried out polymerization after preparing seed emulsion with part (methyl) acrylate monomer and surface active monomer, make polymerization-stable, go out that the quantity of slag is few, gel fraction is low, the modified acrylate emulsion water-tolerant preparing, and there is outstanding rebound performance, printing coating prepared therefrom has advantages of colour fastness and washing fastness excellence, soft for stamp, is specially adapted to swimming suit stamp.
The technical solution used in the present invention is:
A preparation method for modified acrylate emulsion, the raw materials of described modified acrylate emulsion comprises acrylate, methacrylic ester, vinyl acetate, vinyl cyanide, vinylformic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer;
Described acrylate is that alkyl carbon number is one or more in 2～4 alkyl acrylate, described methacrylic ester is that alkyl carbon number is one or more in 1～4 alkyl methacrylate, described organic-silicon-modified monomer is to contain and the line style organopolysiloxane of the alkenyl of silicon bonding, 25 DEG C of viscositys are 1000-5000mPas, and alkenyl mass content is 0.05-0.5%;
Described preparation method comprises preparation, the preparation of seed emulsion and the preparation process of polymer emulsion of pre-emulsion:
The preparation of pre-emulsion: after getting acrylate and/or methacrylic ester and mixing with organic-silicon-modified monomer, be added to the water emulsification, add again vinyl acetate, vinyl cyanide, vinylformic acid, cross-linking monomer, acrylate, methacrylic ester to carry out emulsification, obtain pre-emulsion;
The preparation of seed emulsion: prepare seed emulsion with acrylate and/or methacrylic ester, surface active monomer;
The preparation of polymer emulsion: drip pre-emulsion to seed emulsion and carry out letex polymerization, obtain modified acrylate emulsion.
Modified acrylate emulsion of the present invention is obtained through letex polymerization by acrylate, methacrylic ester, vinyl acetate, vinyl cyanide, vinylformic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer.Described acrylate is one or more in alkyl acrylate, and wherein alkyl is that carbon number is 2～4 alkyl, comprises ethyl, n-propyl, normal-butyl, isobutyl-or sec-butyl.Described methacrylic ester is that alkyl carbon number is one or more in 1～4 alkyl methacrylate, and described alkyl comprises methyl, ethyl or normal-butyl.
First the present invention falls organic-silicon-modified monomer after glutinous and carries out emulsification again with the acrylate in raw materials and/or methacrylic ester mixed diluting, improve emulsification and polymeric modification effect, be in the preparation process of pre-emulsion, first carrying out the dilution of organic-silicon-modified monomer falls glutinous, can adopt acrylate to mix as thinner with methacrylic ester, or adopt acrylate as thinner, or adopt methacrylic ester as thinner.The consumption of thinner is not limit, and organic-silicon-modified monomer can be diluted to compared with low-viscosity.Preferably, described in get after acrylate and/or methacrylic ester mix with organic-silicon-modified monomer and obtain mixture, mixture is 20～50mPas at the viscosity of 25 DEG C.Preferred, in the preparation process of pre-emulsion, the acrylate that described and organic-silicon-modified monomer adopts comprises n-butyl acrylate.
Preferably, in the preparation process of seed emulsion, the temperature of reaction that described preparation process adopts is 70～75 DEG C, and the time is 10-20min.
Preferably, in the preparation process of described seed emulsion, the quality of acrylate and/or methacrylic ester is the 2-7% of acrylate and methacrylic ester quality sum in described acrylic ester emulsion raw materials, to slow down polymerization exotherm, reacting balance is carried out.
Preferably, in the preparation process of seed emulsion, monomer used comprises acrylate.
More preferably, in the preparation process of seed emulsion, monomer used comprises acrylate and methacrylic ester, and the quality of described acrylate accounts for described acrylate and the more than 50% of methacrylic ester quality sum.
Preferably, in the preparation process of seed emulsion, described acrylate comprises ethyl propenoate, and described methacrylic ester comprises methyl methacrylate, makes seed emulsion have good polymerization stability.
25 DEG C of viscositys of the present invention are sample the coefficient of dynamic viscosity value of 25 DEG C.Described containing with the molecular structure of the line style organopolysiloxane of the alkenyl of silicon bonding in, alkenyl comprises vinyl, propenyl, butenyl or allyl group, is preferably vinyl.Preferred, described alkenyl is positioned at the molecular end of line style organopolysiloxane, comprises that end-vinyl polydimethylsiloxane and end-vinyl gather ethylene methacrylic radical siloxane.The quality percentage composition that described alkenyl mass content is alkenyl in organic-silicon-modified monomer, alkenyl is vinyl mass content while being vinyl.
Preferably, described containing with the molecular structure of the line style organopolysiloxane of the alkenyl of silicon bonding in, also comprise methyl and/or phenyl with the organic radical of silicon bonding.
Preferably, described surface active monomer is anionic surface activity monomer, concrete material is not limit, can be sodium vinyl sulfonate, 2-acrylamide-2-methylpro panesulfonic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, double bond containing polyether thiourea hydrochlorate, the double bond containing pair of alkyl sulfosuccinate ester salt, 2-acrylamide-2, one or more in 2-dimethyl ethyl sulfonic acid sodium.Wherein, double bond containing polyether thiourea hydrochlorate can be NRS-10, the V-10S etc. of the loyal Fine Chemical Co., Ltd in Shanghai, can be NRS-138, the M-10S etc. of the loyal Fine Chemical Co., Ltd in Shanghai containing two alkyl sulfosuccinate ester salts of two key bases.
Preferably, described modified acrylate emulsion is by comprising that following monomer by mass percentage prepares:
The molecular end that is described end-vinyl polydimethylsiloxane all contains the polydimethylsiloxane with the vinyl of silicon bonding.
When the cross-linking monomer that described modified acrylate emulsion adopts comprises glycidyl methacrylate, diacetone-acryloamide(DAA) and adipic dihydrazide, can make emulsion realize at normal temperatures crosslinked film forming, emulsion can improve stamp colour fastness and washing fastness for the preparation of printing coating.
In the preparation process of described polymer emulsion, the condition of described letex polymerization, without particular restriction, comprises conventional adding initiator and be added dropwise to complete rear temperature reaction, carries out the elimination of residual monomer after having reacted, the operations such as cooling and adjusting pH to 7～8.
Beneficial effect of the present invention:
The present invention adopts improved emulsion polymerization, taking acrylate, methacrylic ester, vinyl acetate, vinyl cyanide, vinylformic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer as polymerization single polymerization monomer, prepare the modification acrylate stamp emulsion of good stability, this polymerization process has advantages of polymerization-stable, slag yield is low, gel fraction is low (lower than 0.1%), particle diameter little (being less than 100nm), and method is simple, safety and environmental protection, is convenient to industrialization.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvement and differentiation, these improvement and differentiation are also considered as protection scope of the present invention.
Embodiment 1
Prepare modified acrylate emulsion, comprise following operation steps:
30g n-butyl acrylate, 30g methyl methacrylate and 30g end-vinyl polydimethylsiloxane are stirred, obtain the mixture that 25 DEG C of viscositys are 20mPas; Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane is that 0.2%, 25 DEG C of viscosity is 1500mPas;
Mixture, n-butyl acrylate 145g, vinyl acetate 110g, methyl methacrylate 55g, vinyl cyanide 40g, vinylformic acid 6g, glycidyl methacrylate 10g, diacetone-acryloamide(DAA) 5g, adipic dihydrazide 4g are added in the 180g water that contains 3g emulsifying agent and carry out pre-emulsification, obtain pre-emulsion; Wherein, 3:5 is composite in mass ratio obtains by the EmulsogenEPA073 of Clarient and the Emulsogen LXN407 of Clarient for emulsifying agent;
After being mixed with 280g water, 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent be warming up to 75 DEG C, after adding 10g ethyl propenoate and 8g ammonium persulfate solution (mass concentration is 5%), react 12min at 75 DEG C, there is blue light to reaction system, obtain seed emulsion;
Seed emulsion is warming up to 85 DEG C, drip pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), time for adding is 3h, and in dropping process, controlling temperature is 85 DEG C, again in 85 DEG C of isothermal reaction 1h, add the reactant aqueous solution 20min containing vitamins C and oxygenant tertbutyl peroxide, be cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, be cooled to room temperature, add ammoniacal liquor and regulate pH to 8,200 order copper mesh filter, and obtain modified acrylate emulsion.
Wherein, be 6% containing the total mass concentration of vitamins C and oxygenant tertbutyl peroxide in the aqueous solution of vitamins C and oxygenant tertbutyl peroxide, the mass ratio of vitamins C and oxygenant tertbutyl peroxide is 1:1.25.
In above preparation method, adding ammoniacal liquor adjusting pH backsight is that polyreaction finishes, obtain reaction solution, the gel fraction of test polymerization, method is: with 200 order copper mesh filtering reacting liquids, filtrate is modification acrylate stamp emulsion, collect the gelatinous mass on filter residue and reactor, agitator, gel water is rinsed and is placed on for 3-5 time in watch-glass, put into moisture eliminator and dry 2h in 120 DEG C, calculated for gel rate after weighing, calculation formula is:
In formula, m
0for monomer total mass, m
1for dried gel quality affects.
Another test unit transformation efficiency: get 1-2g reaction solution and be placed in weighing bottle, splash into mass percent and be 5% Resorcinol aqueous solution 2-3 and drip, put into baking oven and be dried to constant weight in 110-120 DEG C, calculate monomer conversion, calculation formula is:
M '
0for reaction solution quality, g; M '
1for the constant weight quality after samples dried, g; m
alwaysfor the total mass that feeds intake, g; m
nofor the quality of the middle nonvolatile substances that feeds intake, g; m
singlefor monomer total mass, g.
It is 0.03% that test obtains gel fraction, and monomer conversion is 98.6%, adopts the particle diameter D of latex particle in Ou Qiao emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion
50for 60nm.
Embodiment 2
Prepare modified acrylate emulsion, comprise following operation steps:
30g n-butyl acrylate, 50g methyl methacrylate and 40g end-vinyl polydimethylsiloxane are stirred, obtain the mixture that 25 DEG C of viscositys are 20mPas; Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane is that 0.3%, 25 DEG C of viscosity is 1000mPas;
Described mixture, n-butyl acrylate 200g, vinyl acetate 75g, methyl methacrylate 20g, vinyl cyanide 20g, vinylformic acid 9g, glycidyl methacrylate 8g, diacetone-acryloamide(DAA) 6g, adipic dihydrazide 4.8g are added in the 180g water that contains 4g emulsifying agent and carry out pre-emulsification, obtain pre-emulsion; Wherein, 1:2 is composite in mass ratio obtains by the EmulsogenEPA073 of Clarient and the Emulsogen LXN407 of Clarient for emulsifying agent;
After being mixed with 280g water, allyloxy hydroxypropyl azochlorosulfonate acid sodium 1g, emulsifying agent 2g be warming up to 75 DEG C, after adding 14g ethyl propenoate and 10g ammonium persulfate solution (mass concentration is 5%), react 18min at 75 DEG C, there is blue light to reaction system, obtain seed emulsion;
Seed emulsion is warming up to 86 DEG C, drip pre-emulsion and 40g ammonium persulfate solution (mass concentration is 5%), time for adding is 3.5h, and in dropping process, controlling temperature is 86 DEG C, again in 86 DEG C of isothermal reaction 1h, add the reactant aqueous solution 20min containing vitamins C and oxygenant tertbutyl peroxide, be cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, be cooled to room temperature, add ammoniacal liquor and regulate pH to 8,200 order copper mesh filter, and obtain modified acrylate emulsion.
Wherein, be 6% containing the total mass concentration of vitamins C and oxygenant tertbutyl peroxide in the aqueous solution of vitamins C and oxygenant tertbutyl peroxide, the mass ratio of vitamins C and oxygenant tertbutyl peroxide is 1:1.3.
Obtaining gel fraction by the method test of embodiment 1 is 0.05%, and monomer conversion is 98.3%, and adopts the particle diameter D of latex particle in Ou Qiao emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion
50for 80nm.
Embodiment 3
Prepare modified acrylate emulsion, comprise following operation steps:
40g n-butyl acrylate, 20g methyl methacrylate and end-vinyl polydimethylsiloxane 30g are stirred, obtain the mixture that 25 DEG C of viscositys are 20mPas; Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane is that 0.4%, 25 DEG C of viscosity is 1500mPas;
Said mixture, n-butyl acrylate 170g, vinyl acetate 100g, methyl methacrylate 60g, vinyl cyanide 20g, vinylformic acid 6g, glycidyl methacrylate 10g, diacetone-acryloamide(DAA) 5g, adipic dihydrazide 4g are added in the 180g water that contains 3g emulsifying agent and carry out pre-emulsification, obtain pre-emulsion; Wherein, 3:5 is composite in mass ratio obtains by the EmulsogenEPA073 of Clarient and the Emulsogen LXN407 of Clarient for emulsifying agent;
After being mixed with 280g water, 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent be warming up to 75 DEG C, after adding 8g ethyl propenoate, 6g methyl methacrylate and 8g ammonium persulfate solution (mass concentration is 5%), react 12min at 75 DEG C, there is blue light to reaction system, obtain seed emulsion;
Seed emulsion is warming up to 85 DEG C, drip pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), time for adding is 3h, and in dropping process, controlling temperature is 85 DEG C, again in 85 DEG C of isothermal reaction 1h, add the reactant aqueous solution 20min containing vitamins C and oxygenant tertbutyl peroxide, be cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, be cooled to room temperature, add ammoniacal liquor and regulate pH to 8,200 order copper mesh filter, and obtain modified acrylate emulsion.
Wherein, be 6% containing the total mass concentration of vitamins C and oxygenant tertbutyl peroxide in the aqueous solution of vitamins C and oxygenant tertbutyl peroxide, the mass ratio of vitamins C and oxygenant tertbutyl peroxide is 1:1.25.
Obtaining gel fraction by the method test of embodiment 1 is 0.03%, and monomer conversion is 98.8%, and adopts the particle diameter D of latex particle in Ou Qiao emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion
50for 80nm.
Embodiment 4
Prepare modified acrylate emulsion, comprise following operation steps:
60g n-butyl acrylate and end-vinyl polydimethylsiloxane 30g are stirred, obtain the mixture that 25 DEG C of viscositys are 20mPas; Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane is that 0.4%, 25 DEG C of viscosity is 2000mPas;
Said mixture, n-butyl acrylate 140g, vinyl acetate 105g, methyl methacrylate 80g, vinyl cyanide 25g, vinylformic acid 6g, glycidyl methacrylate 10g, diacetone-acryloamide(DAA) 5g, adipic dihydrazide 4g are added in the 180g water that contains 3g emulsifying agent and carry out pre-emulsification, obtain pre-emulsion; Wherein, 3:5 is composite in mass ratio obtains by the EmulsogenEPA073 of Clarient and the Emulsogen LXN407 of Clarient for emulsifying agent;
After being mixed with 280g water, 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent be warming up to 75 DEG C, after adding 5g ethyl propenoate, 6g methyl methacrylate, 4g n-butyl acrylate and 8g ammonium persulfate solution (mass concentration is 5%), react 12min at 75 DEG C, there is blue light to reaction system, obtain seed emulsion;
Seed emulsion is warming up to 85 DEG C, drip pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), time for adding is 3h, and in dropping process, controlling temperature is 85 DEG C, again in 85 DEG C of isothermal reaction 1h, add the reactant aqueous solution 20min containing vitamins C and oxygenant tertbutyl peroxide, be cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, be cooled to room temperature, add ammoniacal liquor and regulate pH to 8,200 order copper mesh filter, and obtain modified acrylate emulsion.
Wherein, be 6% containing the total mass concentration of vitamins C and oxygenant tertbutyl peroxide in the aqueous solution of vitamins C and oxygenant tertbutyl peroxide, the mass ratio of vitamins C and oxygenant tertbutyl peroxide is 1:1.25.
Obtaining gel fraction by the method test of embodiment 1 is 0.025%, and monomer conversion is 99.1%, and the particle diameter D50 that adopts Ou Qiao emulsion particle diameter morphology analysis instrument (model FC200S) to test latex particle in emulsion is 60nm.
Comparative example
Adopt conventional emulsion polymerization legal system for modified acrylate emulsion, concrete operation step comprises:
N-butyl acrylate 220g, ethyl propenoate 10g, vinyl acetate 100g, methyl methacrylate 70g, vinyl cyanide 20g, vinylformic acid 6g, end-vinyl polydimethylsiloxane 30g, glycidyl methacrylate 10g, diacetone-acryloamide(DAA) 5g, adipic dihydrazide 4g, allyloxy hydroxypropyl azochlorosulfonate acid sodium 2g are added in the 460g water that contains 8g emulsifying agent and carry out pre-emulsification, obtain pre-emulsion;
Take out 4/5 pre-emulsion, 8g ammonium persulfate solution (mass concentration is 5%) is added in remaining 1/5 pre-emulsion, be warming up to 75 DEG C of isothermal reaction 15min, after appearring in reaction system, blue light is warming up to 85 DEG C, drip 4/5 pre-emulsion and the 32g ammonium persulfate solution (mass concentration is 5%) that take out, time for adding is 3h, in dropping process, controlling temperature is 85 DEG C, again in 85 DEG C of isothermal reaction 2h, add the reactant aqueous solution 20min containing vitamins C and oxygenant tertbutyl peroxide, be cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, be cooled to room temperature, add ammoniacal liquor and regulate pH to 8, 200 order copper mesh filter, obtain contrasting modified acrylate emulsion.
Wherein, end-vinyl polydimethylsiloxane, emulsifying agent, identical with embodiment 1 containing the aqueous solution of vitamins C and oxygenant tertbutyl peroxide.
Obtaining gel fraction by the method test of embodiment 1 is 0.32%, and monomer conversion is 95.6%, and adopts the particle diameter D of latex particle in Ou Qiao emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion
50for 260nm.
Test implementation example
One, the modified acrylate emulsion (being called for short stamp emulsion) embodiment 1～4 being prepared, emulsion and commercial acrylate emulsion (being called for short commercially available) prepared by comparative example are carried out performance test, and method is as follows:
Calcium ion stability: add 5ml emulsion in the test tube of 10ml scale, then adding 5ml massfraction is 5% CaCl
2the aqueous solution, is positioned on test-tube stand after shaking up, and after standing 48h, the phenomenons such as layering, precipitation, flocculation does not occur, and being designated as Calcium ion stability passes through;
According to the mechanical stability of GB/T20623-2006 test emulsion;
According to the package stability of GB/T11175-2002 " synthetic resin emulsion test method " test emulsion;
Water resistance test: emulsion is evenly coated on glass with film preparing device, room temperature leaves standstill one day, then puts into 50 DEG C of loft drier inner dryings 6 hours, after taking-up is cooled to room temperature, is dipped in water, 2/3 latex film is dipped in water, observes the time that film turns white and comes off;
Tensile strength, elongation at break: emulsion is spread on ptfe plastic plate at drying at room temperature 48h, obtain the glued membrane that thickness is 1mm, glued membrane is peeled off and cut into dumbbell shaped, on XL-2500 shaped material trier, test its tensile strength and elongation at break;
Rebound resilience: emulsion is spread on ptfe plastic plate at drying at room temperature 48h, obtain the glued membrane that thickness is 1mm, glued membrane is peeled off and cut into dumbbell shaped, on XL-2500 shaped material trier, be stretched to 400% elongation, stop stretching and taking off glued membrane, leave standstill constant to glued membrane after, length before and after test glued membrane stretches on draw direction, calculates rebound degree, and rebound degree is glued membrane length and the rear glued membrane length ratio that stretches before stretching, numerical value is higher, and rebound performance is better.
Test result is in table 1, table 2.
Table 1
Table 2
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example | Commercially available |
| Tensile strength/MPa | 1.0 | 1.2 | 1.1 | 1.2 | 1.2 | 1.0 |
| Elongation at break/% | 800 | 600 | 650 | 750 | 650 | 600 |
| Rebound degree/% | 99.6 | 99.8 | 99.8 | 99.7 | 98.1 | 90.3 |
From table 1 and table 2 data, the present invention has satisfactory stability and water tolerance with the emulsion of the preparations such as organic-silicon-modified monomer and surface active monomer, with commercial acrylate stamp emulsion comparison, after film forming, especially there is good rebound performance, be particularly useful for the stamp of swimming suit fabric.
Two, the modified acrylate emulsion (abbreviation emulsion) preparing with embodiment 1～4, emulsion prepared by comparative example and commercial acrylate stamp emulsion (being called for short commercially available) are prepared respectively printing paste, and printing paste is carried out to application performance mensuration.
Printing paste is prepared by following material: get PTF thickening material 2g and the water 73g of pigment printing paste (yellow FG in environmental protection coating material mill base 8202, Shanghai labor peace paint company) 5g, emulsion 20g, vapour Bagong department, after mixing, stir, obtain printing paste.
With preparation printing paste carry out stamp, treating to adopt conventional platform version screen printing technique to carry out stamp in stamp standard fabric, comprise and stamp-preliminary drying (60 DEG C × 3min)-bake and bank up with earth (120-130 DEG C × 3min) three steps obtain 1-6# PRINTED FABRIC sample.
PRINTED FABRIC sample is carried out to performance measurement, comprising: colour fastness to rubbing is measured by GB/T3920-2008 " textile color stability test colour fastness to rubbing "; Fastness to soaping is pressed GB/T3921-2008 " textile color stability test fastness to soaping " and is measured.
Test result is in table 3.
Table 3
From table 3 data, the printing paste that adopts the modified acrylate emulsion of being prepared by the present invention to prepare carries out after stamp fabric, PRINTED FABRIC has excellent antifriction scrape along fastness to soaping, simultaneously owing to having adopted organosilane monomer to carry out modification, make fabrics feel soft after stamp, and stamp emulsion preparation method is simple, safety and environmental protection, industrialization prospect is good.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a preparation method for modified acrylate emulsion, the raw materials of described modified acrylate emulsion comprises acrylate, methacrylic ester, vinyl acetate, vinyl cyanide, vinylformic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer;
Described acrylate is that alkyl carbon number is one or more in 2～4 alkyl acrylate, described methacrylic ester is that alkyl carbon number is one or more in 1～4 alkyl methacrylate, described organic-silicon-modified monomer is to contain and the line style organopolysiloxane of the alkenyl of silicon bonding, 25 DEG C of viscositys are 1000-5000mPas, and alkenyl mass content is 0.05-0.5%;
Described preparation method comprises preparation, the preparation of seed emulsion and the preparation process of polymer emulsion of pre-emulsion:
The preparation of pre-emulsion: after getting acrylate and/or methacrylic ester and mixing with organic-silicon-modified monomer, be added to the water emulsification, add again vinyl acetate, vinyl cyanide, vinylformic acid, cross-linking monomer, acrylate, methacrylic ester to carry out emulsification, obtain pre-emulsion;
The preparation of seed emulsion: prepare seed emulsion with acrylate and/or methacrylic ester, surface active monomer;
The preparation of polymer emulsion: drip pre-emulsion to seed emulsion and carry out letex polymerization, obtain modified acrylate emulsion.
2. preparation method as claimed in claim 1, is characterized in that, in pre-emulsification step, described in get after acrylate and/or methacrylic ester mix with organic-silicon-modified monomer and obtain mixture, mixture is 20～50mPas at the viscosity of 25 DEG C.
3. preparation method as claimed in claim 1, is characterized in that, in the step of preparation seed emulsion, the temperature of reaction that described preparation process adopts is 70～75 DEG C, and the time is 10-20min.
4. the preparation method as described in claim 1-3 any one, is characterized in that, in the preparation process of pre-emulsion, described and organic-silicon-modified monomer mixes the acrylate adopting and comprises n-butyl acrylate.
5. the preparation method as described in claim 1-3 any one, it is characterized in that, in the preparation process of described seed emulsion, the quality of acrylate and/or methacrylic ester is the 2-7% of acrylate and methacrylic ester quality sum in described acrylic ester emulsion raw materials.
6. the preparation method as described in claim 1-3 any one, is characterized in that, in the preparation process of seed emulsion, monomer used comprises acrylate.
7. preparation method as claimed in claim 6, it is characterized in that, in the preparation process of seed emulsion, monomer used comprises acrylate and methacrylic ester, and the quality of described acrylate accounts for described acrylate and the more than 50% of methacrylic ester quality sum.
8. preparation method as claimed in claim 7, is characterized in that, in the preparation process of seed emulsion, described acrylate comprises ethyl propenoate, and described methacrylic ester comprises methyl methacrylate.
9. the preparation method as described in claim 1-6 any one, described modified acrylate emulsion is by comprising that following monomer by mass percentage prepares:
Described end-vinyl polydimethylsiloxane is that molecular end all contains and the polydimethylsiloxane of the vinyl of silicon bonding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410331416.1A CN104119483B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method of modified acrylate emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410331416.1A CN104119483B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method of modified acrylate emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104119483A true CN104119483A (en) | 2014-10-29 |
| CN104119483B CN104119483B (en) | 2016-10-05 |
Family
ID=51765138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410331416.1A Active CN104119483B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method of modified acrylate emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119483B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001363A (en) * | 2015-06-11 | 2015-10-28 | 深圳市安品有机硅材料有限公司 | Vinyl acetate-acrylic emulsion for printing coating and preparation method thereof |
| CN105603781A (en) * | 2016-01-25 | 2016-05-25 | 苏州印丝特纺织数码科技有限公司 | Preparing method for modified acrylate emulsion and application of modified acrylate emulsion to pigment printing |
| CN106496451A (en) * | 2016-12-15 | 2017-03-15 | 上海雅运纺织助剂有限公司 | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof |
| CN108314755A (en) * | 2018-03-06 | 2018-07-24 | 中山大学 | A kind of environment-protection coating printing adhesive lotion and its preparation method and application |
| CN108359046A (en) * | 2018-02-01 | 2018-08-03 | 广州市斯洛柯高分子聚合物有限公司 | A kind of organosilicon-modified acrylic emulsion and preparation method thereof |
| CN109440500A (en) * | 2018-10-31 | 2019-03-08 | 潢川县圣宇服饰科技有限公司 | High definition silk-screen printing technique and its application on compound fabric stamp |
| CN110003482A (en) * | 2019-04-24 | 2019-07-12 | 常州大学 | A kind of polyacrylate dispersion and preparation method thereof towards plastic basis material |
| CN110581247A (en) * | 2018-06-08 | 2019-12-17 | 上海恩捷新材料科技股份有限公司 | Ceramic composite diaphragm and preparation method thereof |
| CN111058334A (en) * | 2019-12-26 | 2020-04-24 | 无锡达美新材料有限公司 | Modified polyacrylate waterproof anti-sticking agent, preparation method and application |
| CN111285960A (en) * | 2020-04-17 | 2020-06-16 | 江门市金桥新材料有限公司 | Acrylic emulsion and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN101974299A (en) * | 2010-10-11 | 2011-02-16 | 新丰杰力电工材料有限公司 | High temperature-resistant polyacrylate pressure-sensitive adhesive emulsion and preparation method and application thereof |
| CN103483493A (en) * | 2013-09-18 | 2014-01-01 | 广州中国科学院工业技术研究院 | Silicone modified acrylic ester emulsion and preparation method thereof |
-
2014
- 2014-07-11 CN CN201410331416.1A patent/CN104119483B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN101974299A (en) * | 2010-10-11 | 2011-02-16 | 新丰杰力电工材料有限公司 | High temperature-resistant polyacrylate pressure-sensitive adhesive emulsion and preparation method and application thereof |
| CN103483493A (en) * | 2013-09-18 | 2014-01-01 | 广州中国科学院工业技术研究院 | Silicone modified acrylic ester emulsion and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张庆轩等: "有机硅-丙烯酸酯聚合乳液合成及粒径分析", 《化学研究与应用》, vol. 22, no. 4, 30 April 2010 (2010-04-30) * |
| 牛松: "据丙烯酸酯无皂乳液的合成及应用研究", 《中国优秀硕士论文全文数据库工程科技Ⅰ辑》, no. 3, 15 March 2011 (2011-03-15) * |
| 陈立军等: "预乳化半连续种子乳液聚合制备聚合物水泥防水涂料用丙烯酸酯乳液", 《新型建筑材料》, no. 08, 25 August 2005 (2005-08-25) * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001363A (en) * | 2015-06-11 | 2015-10-28 | 深圳市安品有机硅材料有限公司 | Vinyl acetate-acrylic emulsion for printing coating and preparation method thereof |
| CN105603781A (en) * | 2016-01-25 | 2016-05-25 | 苏州印丝特纺织数码科技有限公司 | Preparing method for modified acrylate emulsion and application of modified acrylate emulsion to pigment printing |
| CN105603781B (en) * | 2016-01-25 | 2018-05-15 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of modified acrylate emulsion and the application in pigment printing |
| CN106496451A (en) * | 2016-12-15 | 2017-03-15 | 上海雅运纺织助剂有限公司 | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof |
| CN108359046A (en) * | 2018-02-01 | 2018-08-03 | 广州市斯洛柯高分子聚合物有限公司 | A kind of organosilicon-modified acrylic emulsion and preparation method thereof |
| CN108314755A (en) * | 2018-03-06 | 2018-07-24 | 中山大学 | A kind of environment-protection coating printing adhesive lotion and its preparation method and application |
| CN110581247A (en) * | 2018-06-08 | 2019-12-17 | 上海恩捷新材料科技股份有限公司 | Ceramic composite diaphragm and preparation method thereof |
| CN109440500A (en) * | 2018-10-31 | 2019-03-08 | 潢川县圣宇服饰科技有限公司 | High definition silk-screen printing technique and its application on compound fabric stamp |
| CN109440500B (en) * | 2018-10-31 | 2020-12-29 | 潢川县圣宇服饰科技有限公司 | High-definition screen printing process and application thereof in composite fabric printing |
| CN110003482A (en) * | 2019-04-24 | 2019-07-12 | 常州大学 | A kind of polyacrylate dispersion and preparation method thereof towards plastic basis material |
| CN110003482B (en) * | 2019-04-24 | 2021-04-30 | 常州大学 | Polyacrylate emulsion for plastic base material and preparation method thereof |
| CN111058334A (en) * | 2019-12-26 | 2020-04-24 | 无锡达美新材料有限公司 | Modified polyacrylate waterproof anti-sticking agent, preparation method and application |
| CN111058334B (en) * | 2019-12-26 | 2022-04-22 | 无锡达美新材料有限公司 | Modified polyacrylate waterproof anti-sticking agent, preparation method and application |
| CN111285960A (en) * | 2020-04-17 | 2020-06-16 | 江门市金桥新材料有限公司 | Acrylic emulsion and application thereof |
| CN111285960B (en) * | 2020-04-17 | 2021-10-01 | 江门市金桥新材料有限公司 | Acrylic emulsion and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104119483B (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119483A (en) | Preparing method of modified acrylate emulsion | |
| CN104109975B (en) | Modification acrylate stamp emulsion and preparation method thereof | |
| CN102127186B (en) | Method for preparing fluorine-containing silicon acrylate emulsion | |
| CN101928367B (en) | Environmentally-friendly acrylic ester coating printing adhesive emulsion and preparation method | |
| CN102199239B (en) | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure | |
| CN105131174B (en) | It is common to lasting uvioresistant finishing agent of cotton and terylene and preparation method thereof | |
| CN105111363B (en) | A kind of function performed polymer and preparation method and application | |
| CN104672403A (en) | Environment-friendly silicon-acrylate emulsion and preparation method thereof | |
| CN104831540A (en) | Water-repellent, oil-repellent, sun-proof, anti-bend torsion and cold-resistant matt-leather-membrane aqueous coating adhesive for textiles and preparation method of matt-leather-membrane aqueous coating adhesive | |
| CN102702437A (en) | Styrene-acrylic emulsion as well as preparation method and application thereof | |
| CN106118314A (en) | Modified urethane acrylate water-borne wood latex and preparation method thereof | |
| CN109281172A (en) | Hud typed free-floride water-proof aagent and its preparation method and application | |
| CN107964060A (en) | A kind of gradient type polyacrylate stamp lotion and preparation method thereof | |
| CN103333284A (en) | Silicone acrylic emulsion and application of silicone acrylic emulsion as textile finishing agent | |
| CN109796554A (en) | A kind of elastic emulsion and preparation method thereof for zero titanium system | |
| CN108589343A (en) | A kind of preparation method and application of pigment/organosilicon of multi-layer core-shell structure/polyacrylate Na capsule coating | |
| CN109680522A (en) | A kind of research of silicone modified coating printing paste used for textiles and preparation method | |
| CN106496451A (en) | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof | |
| CN109370287A (en) | A kind of hydrogel being sustained silicone oil and its application in marine antifouling coating | |
| CN109322165B (en) | A kind of preparation method and application of Waterproof Breathable type cotton fabric coating | |
| CN105862476A (en) | Formaldehyde-free activated dye color fixing agent and preparation method thereof | |
| CN105669942B (en) | A kind of preparation method of polyurethane-modified pigment printing binding agent | |
| CN107476063B (en) | The good water-and acrylate coating adhesive used for textiles and preparation method thereof of soft, cold-resistant, elastic, fastness, resistance to hydrostatic pressure performance | |
| CN103161082A (en) | Organosilicone modification pigment printing adhesion agent and preparation method thereof | |
| CN102108110A (en) | Method for preparing acrylate printing adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |