CN104119483B - A kind of preparation method of modified acrylate emulsion - Google Patents
A kind of preparation method of modified acrylate emulsion Download PDFInfo
- Publication number
- CN104119483B CN104119483B CN201410331416.1A CN201410331416A CN104119483B CN 104119483 B CN104119483 B CN 104119483B CN 201410331416 A CN201410331416 A CN 201410331416A CN 104119483 B CN104119483 B CN 104119483B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- acrylate
- preparation
- monomer
- methacrylate
- 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.)
- Active
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention discloses the preparation method of a kind of modified acrylate emulsion, obtained through emulsion polymerization by acrylate, methacrylate, vinylacetate, acrylonitrile, acrylic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer etc., the most organic-silicon-modified monomer is the line style organopolysiloxane containing the alkenyl being bonded with silicon, and be polymerized after preparing seed emulsion with surface active monomer, acrylate and/or methacrylate, emulsifier can be reduced, make polymerization-stable, gel fraction low.
Description
Technical field
The present invention relates to a kind of emulsion polymerisation process, the preparation method of a kind of modified acrylate emulsion.
Background technology
Pigment printing refers to utilize binding agent, by water insoluble, fabric fibre is not had the pigment of affinity and reactivity
Anchor on fabric, realize coloring after drying and forming-film and form the printing method of different patterns.Pigment printing is simple with technique
Low cost, only need to be dried fixation and without washing, save water, electricity, gas after printing, waste water is few, and becomes various fabrics (such as bed
List, singlet, bunting etc.) main method of printing pattern.
Acrylic emulsion is used as stamp emulsion binding agent, has the adhesiveness to pigment, fiber strong, transparent, resistance to
Time property is good, advantage that filming performance is good, but generally there is poor water resistance after acrylate film forming, the low temperature high temperature that becomes fragile becomes glutinous and print
The flower shortcoming that crock fastness is the best, feel is coarse.And in swimming suit printing technology, in use need due to swimming suit to stand
The long period of soaking of water and printing fastness, resistance to water, resistance to bond are had higher requirements, swimming suit uses elastomeric special fabric simultaneously
Make, it is desirable to there is after stamp emulsion film forming good rebound performance, but acrylate printing emulsion of the prior art is difficult to
Meet requirement.
Meanwhile, the preparation of existing acrylic emulsion generally uses semi-continuous emulsion polymerization, including bottoming-intensification cause-
Dropping-insulation-post-treating and other steps, the most first by water, emulsifying agent and part mix monomer and initiator hybrid reaction certain time
Rear dropping residue initiator and mix monomer, continues reaction and terminates to polymerization, the method have polymerization steadily, product is homogeneous, grain
The footpath advantage such as flexibly little, simple to operate, but when water-fast in order to improve after emulsion intercalation method, film forming in acrylic acid synthetic system
Property etc. and when adding reactive emulsifier, easily there is autohemagglutination in reactive emulsifier in participating in polymerization process, it is impossible to fully
Play emulsifiability.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the present invention provides the preparation side of a kind of modified acrylate emulsion
Method, the method is prepared with surface active monomer with part (methyl) acrylate monomer and is polymerized after seed emulsion, makes polymerization
Stable, go out that the quantity of slag is few, gel fraction is low, the modified acrylate emulsion water-tolerant prepared, and there is prominent resilience
Performance, printing coating prepared therefrom has color fastness and excellent, the soft advantage of washing fastness for stamp, the suitableeest
For swimming suit stamp.
The technical solution used in the present invention is:
The preparation method of a kind of modified acrylate emulsion, the raw material of preparing of described modified acrylate emulsion includes propylene
Acid esters, methacrylate, vinylacetate, acrylonitrile, acrylic acid, organic-silicon-modified monomer, cross-linking monomer and surface activity
Monomer；
Described acrylate be alkyl carbon number be one or more in the alkyl acrylate of 2～4, described metering system
Acid esters be alkyl carbon number be one or more in the alkyl methacrylate of 1～4, described organic-silicon-modified monomer is for containing
The line style organopolysiloxane of the alkenyl being bonded with silicon, 25 DEG C of viscositys are 1000-5000mPa s, and alkenyl mass content is
0.05-0.5%；
Described preparation method includes the preparation of pre-emulsion, the preparation of seed emulsion and the preparation process of polymer emulsion:
The preparation of pre-emulsion: take after acrylate and/or methacrylate mix with organic-silicon-modified monomer, add
Emulsifying in water, adds vinylacetate, acrylonitrile, acrylic acid, cross-linking monomer, acrylate, methacrylate carry out breast
Change, obtain pre-emulsion；
The preparation of seed emulsion: prepare seed emulsion with acrylate and/or methacrylate, surface active monomer；
The preparation of polymer emulsion: carry out emulsion polymerization to seed emulsion dropping pre-emulsion, obtain modification acrylate
Emulsion.
The modified acrylate emulsion of the present invention by acrylate, methacrylate, vinylacetate, acrylonitrile, third
Olefin(e) acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer obtain through emulsion polymerization.Described acrylate is acrylic acid
One or more in Arrcostab, wherein alkyl be carbon number be the alkyl of 2～4, including ethyl, n-pro-pyl, normal-butyl, isobutyl group
Or sec-butyl.Described methacrylate be alkyl carbon number be one or more in the alkyl methacrylate of 1～4, institute
State alkyl and include methyl, ethyl or normal-butyl.
First organic-silicon-modified monomer is used and is prepared the acrylate in raw material and/or methacrylate mixing by the present invention
Carry out emulsifying again after dilution fall is glutinous, improve in the preparation process of emulsifying and polymeric modification effect, i.e. pre-emulsion, first have
The dilution fall of machine Si modification monomer is glutinous, acrylate can be used to mix as diluent with methacrylate, or use third
Olefin(e) acid ester is as diluent, or uses methacrylate as diluent.The consumption of diluent does not limits, it is possible to changed by organosilicon
Property monomer is diluted to relatively low-viscosity.Preferably, acrylate and/or methacrylate and organic-silicon-modified list are taken described in
Obtaining mixture after body mixing, mixture is 20～50mPa s at the viscosity of 25 DEG C.It is furthermore preferred that the preparation step of pre-emulsion
In Zhou, the described acrylate used with organic-silicon-modified monomer includes n-butyl acrylate.
Preferably, in the preparation process of seed emulsion, the reaction temperature that described preparation process uses is 70～75 DEG C, the time
For 10-20min.
Preferably, in the preparation process of described seed emulsion, the quality of acrylate and/or methacrylate is described
Acrylic acid ester emulsion prepares acrylate and the 2-7% of methacrylate quality sum in raw material, to slow down polymerization exotherm, makes
Reacting balance is carried out.
Preferably, in the preparation process of seed emulsion, monomer used includes acrylate.
It is highly preferred that in the preparation process of seed emulsion, monomer used includes acrylate and methacrylate, and institute
The quality stating acrylate accounts for described acrylate and more than the 50% of methacrylate quality sum.
Preferably, in the preparation process of seed emulsion, described acrylate includes ethyl acrylate, described methacrylic acid
Ester includes methyl methacrylate, makes seed emulsion have preferable polymerization stability.
25 DEG C of viscositys of the present invention are sample the dynamic viscosity value of 25 DEG C.The described line containing the alkenyl being bonded with silicon
In the molecular structure of type organopolysiloxane, alkenyl includes vinyl, acrylic, cyclobutenyl or pi-allyl, preferably ethylene
Base.It is furthermore preferred that described alkenyl is positioned at the molecular end of line style organopolysiloxane, including end-vinyl polydimethylsiloxanes
Alkane and end-vinyl Polymethyl methacrylate.Described alkenyl mass content is the matter of organic-silicon-modified monomer alkenyl groups
Amount percentage composition, alkenyl is to be vinyl mass content during vinyl.
Preferably, in the described molecular structure containing the line style organopolysiloxane of the alkenyl being bonded with silicon, it is bonded with silicon
Organic group also include methyl and/or phenyl.
Preferably, described surface active monomer is anionic surface activity monomer, and concrete material does not limits, and can be vinyl
Sodium sulfonate, 2-acrylamide-2-methylpro panesulfonic acid sodium, allyloxy hydroxypropyl azochlorosulfonate acid sodium, double bond containing polyether thiourea hydrochlorate, contain
Double alkyl sulfosuccinates salt of double bond, 2-acrylamide-2, one or more in 2-dimethyl ethyl sulfonic acid sodium.Wherein,
Double bond containing polyether thiourea hydrochlorate can be NRS-10, V-10S etc. of Shanghai loyalty Fine Chemical Co., Ltd, the double alkane containing double bond base
Base sulfosuccinate ester salt can be NRS-138, M-10S etc. of Shanghai loyalty Fine Chemical Co., Ltd.
Preferably, described modified acrylate emulsion is by including that following monomer by mass percentage prepares:
The molecular end that is described end-vinyl polydimethylsiloxane all contains the poly-diformazan of the vinyl being bonded with silicon
Radical siloxane.
The cross-linking monomer that described modified acrylate emulsion uses includes glycidyl methacrylate, diacetone acrylamide
When amide and adipic dihydrazide, emulsion can be made to realize at normal temperatures cross-linking film forming, emulsion is used for preparing printing coating and can improve
Stamp color fastness and washing fastness.
In the preparation process of described polymer emulsion, the condition of described emulsion polymerization, without particular restriction, adds including conventional
Enter initiator and be added dropwise to complete rear temperature reaction, after having reacted, carrying out the elimination of residual monomer, lower the temperature and regulate pH to 7～
8 operations such as grade.
Beneficial effects of the present invention:
The present invention uses the emulsion polymerization of improvement, with acrylate, methacrylate, vinylacetate, acrylonitrile,
Acrylic acid, organic-silicon-modified monomer, cross-linking monomer and surface active monomer are polymerization monomer, prepare the modification of good stability
Acrylate printing emulsion, this polymerization has polymerization-stable, slag yield is low, gel fraction is low (less than 0.1%), particle diameter is little
The advantage of (less than 100nm), and method is simple, safety and environmental protection, it is simple to industrialization.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvement and differentiation, these improve and differentiation is also considered as
Protection scope of the present invention.
Embodiment 1
Prepare modified acrylate emulsion, including following operating procedure:
By 30g n-butyl acrylate, 30g methyl methacrylate with the stirring of 30g end-vinyl polydimethylsiloxane all
Even, obtain the mixture that 25 DEG C of viscositys are 20mPa s；Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane
Being 0.2%, 25 DEG C of viscositys are 1500mPa s；
By mixture, n-butyl acrylate 145g, vinylacetate 110g, methyl methacrylate 55g, acrylonitrile 40g,
Acrylic acid 6g, glycidyl methacrylate 10g, N-[2-(2-methyl-4-oxopentyl) 5g, adipic dihydrazide 4g add containing 3g breast
The 180g water of agent carries out pre-emulsification, obtains pre-emulsion；Wherein, emulsifying agent is by the EmulsogenEPA073 of Clarient
Compound with the Emulsogen LXN407 3:5 in mass ratio of Clarient and obtain；
It is warming up to 75 DEG C after 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent being mixed homogeneously with 280g water, adds 10g
React 12min at 75 DEG C after ethyl acrylate and 8g ammonium persulfate solution (mass concentration is 5%), to reaction system, indigo plant occurs
Light, obtains seed emulsion；
Seed emulsion is warming up to 85 DEG C, dropping pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), drip
Adding the time is 3h, and controlling temperature during dropping is 85 DEG C, then at 85 DEG C of isothermal reaction 1h, adds containing vitamin C and oxidant
The reactant aqueous solution 20min of tert-butyl hydroperoxide, is cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, is cooled to room temperature, adds
Ammonia regulation pH to 8,200 mesh copper mesh filter, obtain modified acrylate emulsion.
Wherein, vitamin C and oxidant tert-butyl group mistake in the aqueous solution containing vitamin C and oxidant tert-butyl hydroperoxide
The total mass concentration of hydrogen oxide is 6%, and vitamin C is 1:1.25 with the mass ratio of oxidant tert-butyl hydroperoxide.
In method made above, adding ammonia regulation pH backsight is that polyreaction terminates, and obtains reactant liquor, test polymerization
Gel fraction, method is: with 200 mesh copper mesh filtering reacting liquids, filtrate is modification acrylate stamp emulsion, collects filtering residue and anti-
Answer the gelatinous mass on device, agitator, gel water is rinsed and is placed on for 3-5 time in surface plate, put in exsiccator in 120 DEG C
Drying 2h, calculated for gel rate after weighing, computing formula is:
In formula, m0For monomer gross mass, m1For dried gel quality.
Another test unit conversion ratio: take 1-2g reactant liquor and be placed in weighing botle, instill mass percent be 5% to benzene two
Phenol aqueous solution 2-3 drips, and puts into baking oven and is dried to constant weight in 110-120 DEG C, calculates monomer conversion, and computing formula is:
m’0For reactant liquor quality, g；m’1For the constant weight quality after samples dried, g；mAlwaysFor the gross mass that feeds intake, g；mNoFor throwing
The quality of non-volatile matter, g in material；mSingleFor monomer gross mass, g.
It is 0.03% that test obtains gel fraction, and monomer conversion is 98.6%, uses Ou Qiao emulsion particle diameter morphology analysis
The particle diameter D of latex particle in instrument (model FC200S) test emulsion50For 60nm.
Embodiment 2
Prepare modified acrylate emulsion, including following operating procedure:
By 30g n-butyl acrylate, 50g methyl methacrylate with the stirring of 40g end-vinyl polydimethylsiloxane all
Even, obtain the mixture that 25 DEG C of viscositys are 20mPa s；Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane
Being 0.3%, 25 DEG C of viscositys are 1000mPa s；
By described mixture, n-butyl acrylate 200g, vinylacetate 75g, methyl methacrylate 20g, acrylonitrile
20g, acrylic acid 9g, glycidyl methacrylate 8g, N-[2-(2-methyl-4-oxopentyl) 6g, adipic dihydrazide 4.8g add and contain
The 180g water of 4g emulsifying agent carries out pre-emulsification, obtains pre-emulsion；Wherein, emulsifying agent is by Clarient's
The Emulsogen LXN407 1:2 in mass ratio of EmulsogenEPA073 with Clarient is compounding to be obtained；
It is warming up to 75 DEG C after allyloxy hydroxypropyl azochlorosulfonate acid sodium 1g, emulsifying agent 2g and 280g water being mixed homogeneously, adds 14g
React 18min at 75 DEG C after ethyl acrylate and 10g ammonium persulfate solution (mass concentration is 5%), to reaction system, indigo plant occurs
Light, obtains seed emulsion；
Seed emulsion is warming up to 86 DEG C, dropping pre-emulsion and 40g ammonium persulfate solution (mass concentration is 5%), drip
Adding the time is 3.5h, and controlling temperature during dropping is 86 DEG C, then at 86 DEG C of isothermal reaction 1h, adds containing vitamin C and oxidation
The reactant aqueous solution 20min of agent tert-butyl hydroperoxide, is cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, is cooled to room temperature,
Adding ammonia regulation pH to 8,200 mesh copper mesh filter, obtain modified acrylate emulsion.
Wherein, vitamin C and oxidant tert-butyl group mistake in the aqueous solution containing vitamin C and oxidant tert-butyl hydroperoxide
The total mass concentration of hydrogen oxide is 6%, and vitamin C is 1:1.3 with the mass ratio of oxidant tert-butyl hydroperoxide.
Test obtains gel fraction as described in Example 1 is 0.05%, and monomer conversion is 98.3%, and uses Ou Qiao
The particle diameter D of latex particle in emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion50For 80nm.
Embodiment 3
Prepare modified acrylate emulsion, including following operating procedure:
By 40g n-butyl acrylate, 20g methyl methacrylate with end-vinyl polydimethylsiloxane 30g stirring all
Even, obtain the mixture that 25 DEG C of viscositys are 20mPa s；Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane
Being 0.4%, 25 DEG C of viscositys are 1500mPa s；
By said mixture, n-butyl acrylate 170g, vinylacetate 100g, methyl methacrylate 60g, acrylonitrile
20g, acrylic acid 6g, glycidyl methacrylate 10g, N-[2-(2-methyl-4-oxopentyl) 5g, adipic dihydrazide 4g add and contain
The 180g water of 3g emulsifying agent carries out pre-emulsification, obtains pre-emulsion；Wherein, emulsifying agent is by Clarient's
The Emulsogen LXN407 3:5 in mass ratio of EmulsogenEPA073 with Clarient is compounding to be obtained；
It is warming up to 75 DEG C after 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent being mixed homogeneously with 280g water, adds 8g
12min is reacted at 75 DEG C after ethyl acrylate, 6g methyl methacrylate and 8g ammonium persulfate solution (mass concentration is 5%),
To reaction system, blue light occurs, obtain seed emulsion；
Seed emulsion is warming up to 85 DEG C, dropping pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), drip
Adding the time is 3h, and controlling temperature during dropping is 85 DEG C, then at 85 DEG C of isothermal reaction 1h, adds containing vitamin C and oxidant
The reactant aqueous solution 20min of tert-butyl hydroperoxide, is cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, is cooled to room temperature, adds
Ammonia regulation pH to 8,200 mesh copper mesh filter, obtain modified acrylate emulsion.
Wherein, vitamin C and oxidant tert-butyl group mistake in the aqueous solution containing vitamin C and oxidant tert-butyl hydroperoxide
The total mass concentration of hydrogen oxide is 6%, and vitamin C is 1:1.25 with the mass ratio of oxidant tert-butyl hydroperoxide.
Test obtains gel fraction as described in Example 1 is 0.03%, and monomer conversion is 98.8%, and uses Ou Qiao
The particle diameter D of latex particle in emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion50For 80nm.
Embodiment 4
Prepare modified acrylate emulsion, including following operating procedure:
Being stirred with end-vinyl polydimethylsiloxane 30g by 60g n-butyl acrylate, obtaining 25 DEG C of viscositys is
The mixture of 20mPa s；Wherein, the vinyl mass content of end-vinyl polydimethylsiloxane is 0.4%, 25 DEG C of viscositys
For 2000mPa s；
By said mixture, n-butyl acrylate 140g, vinylacetate 105g, methyl methacrylate 80g, acrylonitrile
25g, acrylic acid 6g, glycidyl methacrylate 10g, N-[2-(2-methyl-4-oxopentyl) 5g, adipic dihydrazide 4g add and contain
The 180g water of 3g emulsifying agent carries out pre-emulsification, obtains pre-emulsion；Wherein, emulsifying agent is by Clarient's
The Emulsogen LXN407 3:5 in mass ratio of EmulsogenEPA073 with Clarient is compounding to be obtained；
It is warming up to 75 DEG C after 2g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g emulsifying agent being mixed homogeneously with 280g water, adds 5g
After ethyl acrylate, 6g methyl methacrylate, 4g n-butyl acrylate and 8g ammonium persulfate solution (mass concentration is 5%)
, there is blue light to reaction system, obtain seed emulsion in 75 DEG C of reaction 12min；
Seed emulsion is warming up to 85 DEG C, dropping pre-emulsion and 32g ammonium persulfate solution (mass concentration is 5%), drip
Adding the time is 3h, and controlling temperature during dropping is 85 DEG C, then at 85 DEG C of isothermal reaction 1h, adds containing vitamin C and oxidant
The reactant aqueous solution 20min of tert-butyl hydroperoxide, is cooled to 65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, is cooled to room temperature, adds
Ammonia regulation pH to 8,200 mesh copper mesh filter, obtain modified acrylate emulsion.
Wherein, vitamin C and oxidant tert-butyl group mistake in the aqueous solution containing vitamin C and oxidant tert-butyl hydroperoxide
The total mass concentration of hydrogen oxide is 6%, and vitamin C is 1:1.25 with the mass ratio of oxidant tert-butyl hydroperoxide.
Test obtains gel fraction as described in Example 1 is 0.025%, and monomer conversion is 99.1%, and uses Ou Qi
In emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion difficult to understand, the particle diameter D50 of latex particle is 60nm.
Comparative example
Using conventional emulsion polymerization method to prepare modified acrylate emulsion, concrete operation step includes:
By n-butyl acrylate 220g, ethyl acrylate 10g, vinylacetate 100g, methyl methacrylate 70g, third
Alkene nitrile 20g, acrylic acid 6g, end-vinyl polydimethylsiloxane 30g, glycidyl methacrylate 10g, diacetone acrylamide
Amide 5g, adipic dihydrazide 4g, allyloxy hydroxypropyl azochlorosulfonate acid sodium 2g addition is pre-containing carrying out in the 460g water of 8g emulsifying agent
Emulsifying, obtains pre-emulsion；
Take out the pre-emulsion of 4/5,8g ammonium persulfate solution (mass concentration is 5%) is added remaining 1/5 pre-emulsification
In liquid, it is warming up to 75 DEG C of isothermal reaction 15min, after blue light occurring to reaction system, is warming up to 85 DEG C, the 4/5 pre-breast that dropping is taken out
Changing liquid and 32g ammonium persulfate solution (mass concentration is 5%), time for adding is 3h, and controlling temperature during dropping is 85 DEG C, then
In 85 DEG C of isothermal reaction 2h, add containing vitamin C and the reactant aqueous solution 20min of oxidant tert-butyl hydroperoxide, be cooled to
65 DEG C, at 65 DEG C of isothermal reaction 0.5h again, being cooled to room temperature, add ammonia regulation pH to 8,200 mesh copper mesh filter, obtain contrast and change
Property acrylic acid ester emulsion.
Wherein, end-vinyl polydimethylsiloxane, emulsifying agent, containing vitamin C and oxidant tert-butyl hydroperoxide
Aqueous solution is same as in Example 1.
Test obtains gel fraction as described in Example 1 is 0.32%, and monomer conversion is 95.6%, and uses Ou Qiao
The particle diameter D of latex particle in emulsion particle diameter morphology analysis instrument (model FC200S) test emulsion50For 260nm.
Testing example
One, the modified acrylate emulsion that embodiment 1～4 prepared (being called for short stamp emulsion), comparative example's system
Standby emulsion and commercial acrylate emulsion (being called for short commercially available) carry out performance test, and method is as follows:
Calcium ion stability: adding 5ml emulsion in the test tube of 10ml scale, being subsequently adding 5ml mass fraction is 5%
CaCl2Aqueous solution, is positioned over after shaking up on test tube rack, stand after 48h be not layered, precipitate, the phenomenon such as flocculation, then be designated as calcium
Ion stability passes through；
Mechanical stability according to GB/T20623-2006 test emulsion；
Bin stability according to GB/T11175-2002 " synthetic resin emulsion test method " test emulsion；
Water resistance test: emulsion be spread evenly across on glass with film preparing device, room temperature stands one day, is then placed in
It is dried 6 hours in 50 DEG C of drying baker, takes out and be dipped in water after being cooled to room temperature, the latex film of 2/3 is dipped in water, observe film
The time turned white and come off；
Hot strength, elongation at break: emulsion is spread on ptfe plastic plate in drying at room temperature 48h, obtain thickness
Degree is the glued membrane of 1mm, glued membrane is peeled off and is cut into dumbbell shaped, tests its hot strength on XL-2500 shaped material testing machine
And elongation at break；
Resilience: emulsion is spread on ptfe plastic plate in drying at room temperature 48h, obtain the glued membrane that thickness is 1mm,
Glued membrane peeled off and cuts into dumbbell shaped, XL-2500 shaped material testing machine is stretched to the percentage elongation of 400%, stopping stretching
And take off glued membrane, after standing to glued membrane is constant, tests length in the stretching direction before and after glued membrane stretches, calculate rebound degree, return
Bullet rate is glued membrane length ratio after glued membrane length before stretching and stretching, and numerical value is the highest, and rebound performance is the best.
Test result is shown in Table 1, table 2.
Table 1
Table 2
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example | Commercially available |
| Hot 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 emulsion tool that the present invention is prepared with organic-silicon-modified monomer and surface active monomer etc.
There are good stability and resistance to water, compare with commercial acrylate stamp emulsion, especially there is after film forming good resilience
Can, it is particularly suited for the stamp of swimming suit fabric.
Two, prepared by modified acrylate emulsion (abbreviation emulsion), the comparative example prepared by embodiment 1～4
Emulsion and commercial acrylate stamp emulsion (being called for short commercially available) prepare print paste respectively, and print paste is carried out application performance survey
Fixed.
Print paste is prepared by following material: (yellow FG in environmental protection coating material mill base 8202, Shanghai labor is pacified to take pigment printing paste
Paint company) 5g, emulsion 20g, the PTF thickening agent 2g and water 73g of Ciba, stir after mixing, obtain print paste.
Carry out stamp with the print paste of preparation, treating that in stamp standard fabric, the conventional platform version screen printing technique of employing is entered
Row stamp, including stamp-preliminary drying (60 DEG C × 3min)-bake and bank up with earth (120-130 DEG C × 3min) three steps, obtains 1-6# stamp and knits
Thing sample.
PRINTED FABRIC sample is carried out performance measurement, including: colour fastness to rubbing presses GB/T3920 2008 " textile color
Fastness test colour fastness to rubbing " measure；By GB/T3921 2008, " textile color stability test is resistance to soaps fastness to soaping
Color fastness " measure.
Test result is shown in Table 3.
Table 3
From the data in table 3, it can be seen that use print paste prepared by the modified acrylate emulsion prepared by the present invention to fabric
After carrying out stamp, PRINTED FABRIC has the antifriction scrape along fastness to soaping of excellence, enters simultaneously because have employed organic silicon monomer
Row modification so that fabrics feel soft after stamp, and stamp emulsion preparation method is simple, safety and environmental protection, industrialization prospect is good.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention's
Protection domain.
Claims (9)
1. a preparation method for modified acrylate emulsion, the raw material of preparing of described modified acrylate emulsion includes acrylic acid
Ester, methacrylate, vinylacetate, acrylonitrile, acrylic acid, organic-silicon-modified monomer, cross-linking monomer and surface activity list
Body；
Described acrylate be alkyl carbon number be one or more in the alkyl acrylate of 2～4, described methacrylate
For one or more in alkyl methacrylate that alkyl carbon number is 1～4, described organic-silicon-modified monomer for containing and silicon
The line style organopolysiloxane of the alkenyl of bonding, 25 DEG C of viscositys are 1000-5000mPa s, and alkenyl mass content is
0.05-0.5%；
Described preparation method includes the preparation of pre-emulsion, the preparation of seed emulsion and the preparation process of polymer emulsion:
The preparation of pre-emulsion: take after acrylate and/or methacrylate mix with organic-silicon-modified monomer, be added to the water
Emulsifying, adds vinylacetate, acrylonitrile, acrylic acid, cross-linking monomer, acrylate, methacrylate carry out emulsifying,
To pre-emulsion；
The preparation of seed emulsion: prepare seed emulsion with acrylate and/or methacrylate, surface active monomer；
The preparation of polymer emulsion: carry out emulsion polymerization to seed emulsion dropping pre-emulsion, obtain modified acrylate emulsion.
2. preparation method as claimed in claim 1, it is characterised in that in pre-emulsification step, described in take acrylate and/or first
Base acrylate obtains mixture with organic-silicon-modified monomer after mixing, mixture is 20～50mPa s at the viscosity of 25 DEG C.
3. preparation method as claimed in claim 1, it is characterised in that in the step of preparation seed emulsion, described preparation process
The reaction temperature used is 70～75 DEG C, and the time is 10-20min.
4. the preparation method as described in any one of claim 1-3, it is characterised in that in the preparation process of pre-emulsion, described
Mix the acrylate used with organic-silicon-modified monomer and include n-butyl acrylate.
5. the preparation method as described in any one of claim 1-3, it is characterised in that in the preparation process of described seed emulsion,
The quality of acrylate and/or methacrylate is that described acrylic acid ester emulsion prepares acrylate and metering system in raw material
The 2-7% of acid esters quality sum.
6. the preparation method as described in any one of claim 1-3, it is characterised in that in the preparation process of seed emulsion, used
Monomer includes acrylate.
7. preparation method as claimed in claim 6, it is characterised in that in the preparation process of seed emulsion, monomer used includes
Acrylate and methacrylate, and the quality of described acrylate account for described acrylate and methacrylate quality it
More than the 50% of sum.
8. preparation method as claimed in claim 7, it is characterised in that in the preparation process of seed emulsion, described acrylate
Including ethyl acrylate, described methacrylate includes methyl methacrylate.
9. the preparation method as described in any one of claim 1-3, described modified acrylate emulsion is following by quality by including
The monomer of percentages prepares:
Described end-vinyl polydimethylsiloxane is the polydimethylsiloxanes that molecular end all contains the vinyl being bonded with silicon
Alkane.
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 CN104119483A (en) | 2014-10-29 |
| CN104119483B true 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) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001363B (en) * | 2015-06-11 | 2017-11-28 | 深圳市安品有机硅材料有限公司 | A kind of printing coating acrylate and vinyl acetate emulsion and preparation method thereof |
| 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 |
| CN108314755B (en) * | 2018-03-06 | 2021-03-12 | 中山大学 | Emulsion for environment-friendly pigment printing adhesive and preparation method and application thereof |
| CN110581247B (en) * | 2018-06-08 | 2022-07-22 | 上海恩捷新材料科技有限公司 | Ceramic composite diaphragm and preparation method thereof |
| 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 |
| CN110003482B (en) * | 2019-04-24 | 2021-04-30 | 常州大学 | Polyacrylate emulsion for plastic base material and preparation method thereof |
| 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 |
| 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 |
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 |
|---|
| 据丙烯酸酯无皂乳液的合成及应用研究;牛松;《中国优秀硕士论文全文数据库工程科技Ⅰ辑》;20110315(第3期);20-22 * |
| 有机硅-丙烯酸酯聚合乳液合成及粒径分析;张庆轩等;《化学研究与应用》;20100430;第22卷(第4期);431-435 * |
| 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;陈立军等;《新型建筑材料》;20050825(第08期);1-5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104119483A (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119483B (en) | A kind of preparation method of modified acrylate emulsion | |
| CN104109975B (en) | Modification acrylate stamp emulsion and preparation method thereof | |
| CN101423734B (en) | Method for preparing organosilicon modified acrylic ester binding agent | |
| CN102619103B (en) | Pigment printing imitated reactive printing adhesive 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 | |
| CN105111363B (en) | A kind of function performed polymer and preparation method and application | |
| CN107266626A (en) | A kind of multiple self-crosslinking core-shell type emulsion of room temperature and its preparation method and application | |
| CN104672403A (en) | Environment-friendly silicon-acrylate emulsion and preparation method thereof | |
| CN105949378B (en) | A kind of aqueous acrylic emulsion resin and aqueous coating lotion and preparation method | |
| CN107964060A (en) | A kind of gradient type polyacrylate stamp lotion and preparation method thereof | |
| CN104004146A (en) | Urethane-organic silicon-acrylic ester ternary polymerization emulsion and preparation method thereof | |
| CN110343221A (en) | A kind of anti-adhesion characteristic printing mortar resin and preparation method thereof | |
| CN109796554A (en) | A kind of elastic emulsion and preparation method thereof for zero titanium system | |
| CN106496451A (en) | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof | |
| CN109281172A (en) | Hud typed free-floride water-proof aagent and its preparation method and application | |
| CN105524225A (en) | Core-shell type polyacrylate emulsion printing adhesive | |
| CN109680522A (en) | A kind of research of silicone modified coating printing paste used for textiles and preparation method | |
| CN101698980A (en) | Environmentally-friendly anti-flushing synthetic printing thickener and preparation method thereof | |
| CN105601801A (en) | Preparation process of acrylate resin emulsion having better abrasion-resistant performance and preparation process of corresponding compound printing mucilage | |
| CN107938397A (en) | A kind of cotton fabric strong water-fastness, rub resistance type ink and preparation method thereof | |
| CN105949396B (en) | A kind of water based silicone resin 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 | |
| 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 |