CN105348446A - Preparation method of polystyrene/butyl acrylate-based composite core-shell emulsion and method for preparing high-hardness latex film of polystyrene/butyl acrylate composite core-shell emulsion - Google Patents
Preparation method of polystyrene/butyl acrylate-based composite core-shell emulsion and method for preparing high-hardness latex film of polystyrene/butyl acrylate composite core-shell emulsion Download PDFInfo
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Abstract
A preparation method of a polystyrene/butyl acrylate-based composite core-shell emulsion and a method for preparing a high-hardness latex film of the polystyrene/butyl acrylate composite core-shell emulsion belong to the field of core-shell-structured emulsions, and aim to avoid the defects that a styrene-acrylic emulsion adhesive film is low in tensile strength and poor in hardness and mechanical property. The preparation method comprises the following steps: preparing an St/BA shell emulsion; keeping the temperature of the St/BA shell emulsion to be 80-85 DEG C; dripping shell monomers, and meanwhile, equivalently adding the rest of an initiator water solution in batches at equal time intervals; after finish of dripping of the shell monomers, immediately dripping functional monomers; after finish of dripping of the functional monomers, heating, and keeping the temperature for 30-60 min; cooling to the room temperature; filtering; discharging. The method for preparing the latex film comprises the following steps: taking the polystyrene/butyl acrylate-based composite core-shell emulsion prepared by the preparation method; adding an ionic complexing agent; uniformly stirring; tiling the obtained product at the bottom of concave glassware; drying at the room temperature. The methods are applied to multiple fields of buildings, surface sizing agents, paper-making, coatings, adhesives and the like.
Description
Technical field
The invention belongs to core-shell emulsion field.
Background technology
Benzene emulsion is the product that vinylbenzene and acrylate carry out letex polymerization.Benzene emulsion has had more and more important application in a lot of field in recent years, as building, Surface Size, papermaking, coating, sizing agent etc.Benzene emulsion has certain advantage in guarantor's look, fast light, weather-proof, resistance to oxidation, ultraviolet light resistant etc., but have that tensile strength is lower, low temperature becomes fragile, high temperature becomes the problem such as glutinous, thus limits its application.
How to improve conventional phenylpropyl alcohol glued membrane tensile strength lower, the defect that mechanical property is poor is a key issue prepared by benzene emulsion.Recently, the study on the modification about benzene emulsion has had comparatively quantum jump.As added the functional monomer with carboxyl such as some methylene-succinic acids in emulsion preparation process, make latex surface with carboxylic group, add some linking agents in the curing process, thus certain being cross-linked occurs in emulsion solidification process, thus promote the performance of glued membrane.But simple introducing functional group or add some special linking agents, can only increase the performance of latex film in one aspect.
Summary of the invention
It is low that the present invention will solve benzene emulsion glued membrane tensile strength, difference of hardness, the defect of bad mechanical property, and the present invention, on the basis not affecting the original performance of benzene emulsion, by changing the component of stratum nucleare or shell, realizes the efficient synergy of different components.In preparation process, introduce the functional group of some features simultaneously, after fixing effect is realized to glued membrane, increase the crosslinking degree of glued membrane, thus under inside and outside synergy, improve the tensile strength of latex film greatly, hardness and mechanical property etc.
Of the present invention by the polycomponent core-shell structure styrene-acrylic emulsion of semi-continuous seed emulsion polymerization legal system for the homogeneous dispersion of a kind of small particle size, and pass through the interpolation of ionic complexing agent, prepare and there is better tensile strength, high rigidity, the glued membrane of satisfactory mechanical property, thus improve the performance of benzene emulsion and glued membrane thereof further, expand its range of application.
The preparation method of a kind of polystyrene in the present invention/butyl acrylate base compound core-shell emulsion carries out in the steps below:
Step one, be benchmark by reaction total monomer amount, the mass percentage proportioning of raw material is as follows:
Deionized water: 130% ~ 170%
Butyl acrylate (BA): 30% ~ 45%
Vinylbenzene (St): 20% ~ 50%
Methyl methacrylate (MMA): 0% ~ 35%
Functional monomer: 1.0% ~ 4.0%
Compound emulsifying agent: 3% ~ 5%
Ammonium persulphate: 0.3% ~ 0.6%
NaHCO
3：0.3％～0.8％；
Step 2, step one taken ammonium persulphate and join and account for the ionized water that anhydrates that step one takes deionized water total mass 20%-25% and be made into initiator solution, step one is taken vinylbenzene and account for the butyl acrylate that step one takes butyl acrylate total mass 15%-25% and be mixed to get mix monomer A, the methyl methacrylate mixed configuration shell monomer remaining butyl acrylate and step one taken;
Step 3, in remaining deionized water, add step one take NaHCO
3and compound emulsifying agent, be warming up to 55-65 DEG C, stir 10-20min, add 10% ~ 20% (as seed monomer) mix monomer A of the mix monomer A total mass of step 2 configuration, pre-emulsification 30min, add the initiator solution accounting for step 2 configuration initiator solution total mass 10% ~ 20%, be warming up to 70-80 DEG C, after reaction 25-35min, obtained seed emulsion, then the temperature of seed emulsion is controlled at 70-80 DEG C, dropwise drip remaining mix monomer A (drop rate controls at 0.2ml/min ~ 0.6ml/min) again, equivalent constant duration adds initiator solution in four batches simultaneously, guarantee that mix monomer A dropwises in 2h, final obtained St/BA core emulsion,
Step 4, St/BA core emulsion temperature of reaction obtained for step 3 is maintained 80-85 DEG C, in core emulsion, shell monomer is dripped with the drop rate of 0.4ml/min ~ 1.0ml/min, equivalent constant duration adds remaining initiator solution in six batches simultaneously, after shell monomer dropwises, drip functional monomer to drip the identical drop rate of shell monomer at once, after standby function monomer dropping is complete (time for adding is 3h), be warming up to 85-95 DEG C, insulation 30-60min, be cooled to room temperature, filter discharging; Namely polystyrene/butyl acrylate base compound core-shell emulsion is obtained;
In step 3, when starting to drip mix monomer A, first time adds initiator solution, adds once afterwards every half an hour, and total add-on of initiator solution is 30% ~ 40% of step 2 configuration initiator solution total mass;
In step 4, when starting to drip shell monomer, first time adds initiator solution, adds once afterwards every half an hour.
Compound emulsifying agent described in step one be emulsifier op-10 and sodium laurylsulfonate SDS by (1 ~ 2): mixing of the mass ratio of (1 ~ 3).
Functional monomer described in step one is carboxylic olefin monomer, can select acrylic or methacrylic acid.
The preparation method of polystyrene in the present invention/butyl acrylate base compound core-shell emulsion high rigidity latex film is undertaken by following operation: get polystyrene/butyl acrylate base compound core-shell emulsion prepared by aforesaid method, then ionic complexing agent is added, stir, bottom tiling spill glassware, at room temperature dry 24 ~ 48h, namely obtains high rigidity latex film.
The mol ratio of the function monomer in its ionic complexing agent and polystyrene/butyl acrylate base compound nucleocapsid emulsion materials is (0 ~ 0.5): 1.Described ionic complexing agent is ZnCl
2the aqueous solution, the hexanediamine aqueous solution and CaCl
2the aqueous solution.
Wherein ZnCl
2the mass percent concentration of the aqueous solution is 0.15%-0.45%, CaCl
2the mass percent concentration of the aqueous solution is 0.20%-0.46%, and the mass percent concentration of the hexanediamine aqueous solution is 0,14%-0,40%.
Adopt method disclosed by the invention, with vinylbenzene and butyl acrylate thing for core, methyl methacrylate and butyl acrylate are shell, and a small amount of vinylformic acid is function monomer, successfully prepare and there is small particle size, the hud typed phenylpropyl alcohol polycomponent composite emulsion with specific function group of homogeneous dispersion.This emulsion, under the prerequisite of the fundamental property of original benzene emulsion, by adjusting moiety and the proportioning of emulsion particle, thus improves homogeneous dispersiveness and the filler rigid of particle to a great extent.Meanwhile, adding of functional group and complexing agent, the hardness of latex film, the transparency and water-intake rate can greatly be improved.Benzene emulsion is as a kind of environmental protection, and high performance emulsion, preparation technology is simple, and ambient temperature curable, production cost is low.The hud typed styrene-acrylic composite emulsion of polycomponent prepared by the present invention is nontoxic, and unharmful substance discharges, and latex film intensity is comparatively large, and water-intake rate is lower, can directly be applied in multiple fields such as building, Surface Size, papermaking, coating, sizing agent.
Contrast currently available products, the hud typed styrene-acrylic composite emulsion of polycomponent adopting present method to prepare has the following advantages:
1, latex film strength is higher, and the application in actual paint etc. has greater significance;
2, low in raw material price, preparation technology is simple, very favourable to actual production;
3, latex particle size size is homogeneous, narrow diameter distribution, to bonding property and actual application of size very favourable;
4, the lifting of the hud typed benzene emulsion performance of polycomponent is conducive to the expansion of its Application Areas, expands market;
5, the functionalization of the hud typed benzene emulsion of polycomponent contributes to the application in the field in specific demands such as splicing, coating;
6, this emulsion is nontoxic, without obnoxious flavour release, belongs to environmentally friendly machine;
7, can self-vulcanizing, operation is simple;
8, be directly used as Aqueous Adhesives or coating etc., be applied in multiple fields such as building, Surface Size, papermaking, coating, sizing agent.
Accompanying drawing explanation
Fig. 1 is that (a is not containing MMA for styrene-acrylic composite emulsion infrared spectrum; BMMA content is 29%);
Fig. 2 is composite emulsion DSC curve;
Fig. 3 is scanning electron microscope (SEM) figure of composite emulsion;
Fig. 4 is the latex particle size distribution of the different MMA content of shell, and 1-4 represents that methyl methacrylate (MMA) mass percentage content is respectively: 0%, 5%, 19%, 29%;
Fig. 5 to be MMA content be 29% composite emulsion samples of latex picture;
Fig. 6 to be MMA content be 29% composite emulsion emulsion without the latex film film forming picture of additional after fixing agent;
Fig. 7 latex film film forming picture that to be MMA content be after adding a certain amount of post-reinforcing agent in the composite emulsion emulsion of 29%.
Embodiment
Embodiment one: in present embodiment, the preparation method of a kind of polystyrene/butyl acrylate base compound core-shell emulsion carries out in the steps below:
Step one, be benchmark (namely in butyl acrylate, vinylbenzene, methyl methacrylate and functional monomer total mass for benchmark) by reaction total monomer amount, the mass percentage proportioning of raw material is as follows:
Deionized water: 140%
Butyl acrylate (BA): 30%
Vinylbenzene (St): 30%
Methyl methacrylate (MMA): 0%, 5%, 19% or 29%
Functional monomer: 2.5%
Compound emulsifying agent: 4%
Ammonium persulphate: 0.45%
NaHCO
3：0.5％；
Step 2, step one taken ammonium persulphate and join and account for the ionized water that anhydrates that step one takes deionized water total mass 25% and be made into initiator solution, step one is taken vinylbenzene and account for the butyl acrylate that step one takes butyl acrylate total mass 20% and be mixed to get mix monomer A, the methyl methacrylate mixed configuration shell monomer remaining butyl acrylate and step one taken;
Step 3, in remaining deionized water, add step one take NaHCO
3and compound emulsifying agent, be warming up to 60 DEG C, stir 20min, add 16% (as seed monomer) mix monomer A of the mix monomer A total mass of step 2 configuration, pre-emulsification 30min, add the initiator solution accounting for step 2 configuration initiator solution total mass 20%, be warming up to 75 DEG C, after reaction 30min, obtained seed emulsion, then the temperature of seed emulsion is controlled at 75 DEG C, dropwise drip remaining mix monomer A (drop rate controls at 0.2ml/min ~ 0.6ml/min) again, equivalent constant duration adds initiator solution in four batches simultaneously, guarantee that mix monomer A dropwises in 2h, final obtained St/BA core emulsion,
Step 4, St/BA core emulsion temperature of reaction obtained for step 3 is maintained 80 DEG C, in core emulsion, shell monomer is dripped with the drop rate of 0.4ml/min, equivalent constant duration adds remaining initiator solution in six batches simultaneously, after shell monomer dropwises, drip functional monomer with the drop rate of 0.4ml/min, after standby function monomer dropping is complete (time for adding is about 3h) at once, be warming up to 95 DEG C, insulation 45min, is cooled to room temperature, filters discharging; Namely polystyrene/butyl acrylate base compound core-shell emulsion is obtained;
In step 3, when starting to drip mix monomer A, first time adds initiator solution, adds once afterwards every half an hour, and total add-on of initiator solution is 25% of step 2 configuration initiator solution total mass;
In step 4, when starting to drip shell monomer, first time adds initiator solution, adds once afterwards every half an hour.
The mixing by the mass ratio of 1:3 that be emulsifier op-10 and sodium laurylsulfonate SDS of compound emulsifying agent described in step one.
Functional monomer is vinylformic acid.
Adopt following experimental verification invention effect.
Styrene-acrylic composite emulsion infrared spectrum is shown in Fig. 1, as seen from Figure 1, at 2957.8cm
-1and 2929.6cm
-1there is CH in place
3, CH
2stretching vibration absorption peak; 1728.4cm
-1there is C=O stretching vibration absorption peak at place; 1452.0cm
-1for C-H in-plane bending vibration absorption peak; 1242.1cm
-1, 1158.8cm
-1and 1064.4cm
-1place has obvious stretching vibration absorption peak to think, and on BA, MMA and AA three, C-O superposes peak; At 961.9cm
-1there is the charateristic avsorption band of butyl acrylate in place; 757.0cm
-1and 697.4cm
-1place's absorption peak belongs to single-substituted ethene charateristic avsorption band.By Fig. 1, vinylbenzene, butyl acrylate are described, vinylformic acid and vinylformic acid are present in same system.
Core-shell polymer due to stratum nucleare different from the component of polymer of shell, so there are two different second-order transition temperatures (Tg), and complicated along with emulsion particle moiety, the second-order transition temperature of its second-order transition temperature and pure substance there are differences, and there will be the phenomenon of second-order transition temperature migration.Fig. 2 is the composite emulsion DSC curve of shell MMA content.As seen from Figure 2, there are two obvious second-order transition temperatures in prepared composite emulsion, and the emulsion particle prepared by explanation exists the situation that is significantly separated, thus can have nucleocapsid structure by the emulsion particle prepared by indirect proof.Binding experiment preparation condition, can determine that two second-order transition temperatures correspond respectively to Styrene And Butyl-acrylate stratum nucleare polymkeric substance and the cold zone butyl acrylate-methyl ester sheath polymers of high-temperature zone.
Scanning electron microscope (SEM) analysis is adopted to the pattern of sample.Figure 3 shows that the scanning electron microscope (SEM) photograph of the composite emulsion after dilution 10000 times.As seen from the figure, the emulsion particle structure spherical in shape of composite emulsion, size is homogeneous, is uniformly dispersed, and does not have adhesion between emulsion particle.
In order to confirm the size of emulsion particle further, the Average Particle Diameters of the samples of latex of different MMA content and size distribution are measured.Fig. 4 is the latex particle size distribution of the different MMA content of shell.As can be seen from Figure 4, the size of emulsion particle is homogeneous, and in unimodal distribution, and Average Particle Diameters is 80 ~ 100nm.As shown in Figure 4, when MMA content is 0%, the median size of emulsion particle is about 80nm.With the increase of shell MMA consumption, latex particle size increases gradually.
Fig. 5-7 is samples of latex and film forming picture.Fig. 5 is obtained MMA content is the benzene emulsion of 29%, and emulsion is white, blueing slightly.Fig. 6 and Fig. 7 be respectively without solidifying agent and have solidifying agent condition under obtained latex film.Contrast finds, softer without latex film obtained during solidifying agent, transparency is poor; After adding a certain amount of solidifying agent, the transparency of latex film and hardness have had large increase.
Size and distribution dynamic mechanical light scattering apparatus (DLS, U.S. Brookhaven) thereof measure, and need diluted sample to 0.005-0.01wt% before test.
The hardness of latex film measures according to GB/T6739-2006 " hardness of film pencil assay method ".
The water-intake rate of latex film measures according to ASTMD6015-14 standard.Get latex film sample about 0.01g, it soaked completely to be placed in and deionized water is housed, temperature is in the 1000mL beaker of 23 ± 2 DEG C after 24h, leaching is put sample and takes out, absorbed by surface-moisture before weighing with thieving paper.Often organize at least three samples.Shown in being specifically calculated as follows of water-intake rate:
Wherein, W
1for the quality before water suction, W
2for the quality after water suction.
The results are shown in Table 1
The latex film pencil hardness of the different MMA content of table 1 and water-intake rate.As can be seen from Table 1, along with the increase of MMA content, the pencil hardness change of latex film is not too obvious, and when MMA content is more than 29%, the hardness of latex film is promoted to B from 2B.Along with the increase of MMA content, obviously, water-intake rate is in downward trend gradually for the change of the water-intake rate of latex film.
The latex film pencil hardness of the different MMA content of table 1 and water-intake rate
As shown in Table 1, latex particle size is less, distributes homogeneous.But the water-intake rate of latex film is higher, latex film hardness is poor.
Specific embodiments two: in present embodiment MMA monomer content be 29% (preparation method see specifically mode one), after add the Zn of different content
2+the concrete preparation method of the latex film of ion is as follows:
(1) preparation of latex film
The preparation method of latex film is undertaken by following operation: get polystyrene/butyl acrylate base compound core-shell emulsion prepared by claim aforesaid method, then add Zn
2+(specifically mass percent concentration is the ZnCl of 0.38% to ionic complexing agent
2the aqueous solution), stir, take out 7.5g and be laid in bottom culture dish that (surface-area is 40cm
2), at room temperature dry 24h, namely obtains latex film (thickness is about 400 μm).
(2) performance measurement of latex film
The hardness of latex film measures according to GB/T6739-2006 " hardness of film pencil assay method ".
The water-intake rate of latex film measures according to ASTMD6015-14 standard.Get latex film sample about 0.01g, it soaked completely to be placed in and deionized water is housed, temperature is in the 1000mL beaker of 23 ± 2 DEG C after 24h, leaching is put sample and takes out, absorbed by surface-moisture before weighing with thieving paper.Often organize at least three samples.Shown in being specifically calculated as follows of water-intake rate:
Wherein, W
1for the quality before water suction, W
2for the quality after water suction.
Specific experiment the results are shown in Table 2
Table 2
As shown in Table 2, Zn is not added
2+during as after fixing promotor, the hardness of latex film only has B, and water-intake rate is higher, along with Zn
2+the increase of content, the hardness of latex film increases gradually, maximumly reaches 3H.The water suction of latex film is with Zn
2+the increase of content is in the trend reduced gradually.
Specific embodiments three: in present embodiment MMA monomer content be 29% (preparation method see specifically mode one), after to add the concrete preparation method of the latex film of the hexanediamine of different content as follows:
(1) preparation of latex film
The preparation method of latex film is undertaken by following operation: get polystyrene/butyl acrylate base compound core-shell emulsion prepared by claim aforesaid method, then the hexanediamine aqueous solution that mass percent concentration is 0.33% is added, stir, take out 7.5g and be laid in bottom culture dish that (surface-area is 40cm
2), at room temperature dry 24h, namely obtains latex film (thickness is about 400 μm).
(2) performance measurement of latex film
The hardness of latex film measures according to GB/T6739-2006 " hardness of film pencil assay method ".
The water-intake rate of latex film measures according to ASTMD6015-14 standard.Get latex film sample about 0.01g, it soaked completely to be placed in and deionized water is housed, temperature is in the 1000mL beaker of 23 ± 2 DEG C after 24h, leaching is put sample and takes out, absorbed by surface-moisture before weighing with thieving paper.Often organize at least three samples.Shown in being specifically calculated as follows of water-intake rate:
Wherein, W
1for the quality before water suction, W
2for the quality after water suction.
Specific experiment the results are shown in Table 3
Table 3
As shown in Table 3, when not adding hexanediamine as after fixing promotor, the hardness of latex film only has B, and water-intake rate is higher, and along with the increase of hexanediamine content, the hardness of latex film increases gradually, maximumly reaches 2H.The water suction of latex film with the increase of hexanediamine content in the trend reduced gradually.
Embodiment four: in present embodiment MMA monomer content be 29% (preparation method see specifically mode one), after add the CaCl of different content
2the concrete preparation method of latex film as follows:
(1) preparation of latex film
The preparation method of latex film is undertaken by following operation: get polystyrene/butyl acrylate base compound core-shell emulsion prepared by claim aforesaid method, then add Ca
2+(mass percent concentration is the CaCl of 0.39% to ionic complexing agent
2), stir, take out 7.5g and be laid in bottom culture dish that (surface-area is 40cm
2), at room temperature dry 24h, namely obtains latex film (thickness is about 400 μm).
(2) performance measurement of latex film
The hardness of latex film measures according to GB/T6739-2006 " hardness of film pencil assay method ".
The water-intake rate of latex film measures according to ASTMD6015-14 standard.Get latex film sample about 0.01g, it soaked completely to be placed in and deionized water is housed, temperature is in the 1000mL beaker of 23 ± 2 DEG C after 24h, leaching is put sample and takes out, absorbed by surface-moisture before weighing with thieving paper.Often organize at least three samples.Shown in being specifically calculated as follows of water-intake rate:
Wherein, W
1for the quality before water suction, W
2for the quality after water suction.
Specific experiment the results are shown in Table 4
Table 4
As shown in Table 4, Ca is not added
2+during as after fixing promotor, the hardness of latex film only has B, and water-intake rate is higher, along with Ca
2+the increase of content, the hardness of latex film increases gradually, maximumly reaches 2H.The water suction of latex film is with Ca
2+the increase of content is in the trend reduced gradually.
Claims (10)
1. a preparation method for polystyrene/butyl acrylate base compound core-shell emulsion, is characterized in that this preparation method carries out in the steps below:
Step one, be benchmark by reaction total monomer amount, the mass percentage proportioning of raw material is as follows:
Deionized water: 130% ~ 170%
Butyl acrylate: 30% ~ 45%
Vinylbenzene: 20% ~ 50%
Methyl methacrylate: 0% ~ 35%
Functional monomer: 1.0% ~ 4.0%
Compound emulsifying agent: 3% ~ 5%
Ammonium persulphate: 0.3% ~ 0.6%
NaHCO
3：0.3％～0.8％；
Step 2, step one taken ammonium persulphate and join and account for the ionized water that anhydrates that step one takes deionized water total mass 20%-25% and be made into initiator solution, step one is taken vinylbenzene and account for the butyl acrylate that step one takes butyl acrylate total mass 15%-25% and be mixed to get mix monomer A, the methyl methacrylate mixed configuration shell monomer remaining butyl acrylate and step one taken;
Step 3, in remaining deionized water, add step one take NaHCO
3and compound emulsifying agent, be warming up to 55-65 DEG C, stir 10-20min, add 10% ~ 20% mix monomer A of the mix monomer A total mass of step 2 configuration, pre-emulsification 30min, add the initiator solution accounting for step 2 configuration initiator solution total mass 10% ~ 20%, be warming up to 70-80 DEG C, after reaction 25-35min, obtained seed emulsion, then the temperature of seed emulsion is controlled at 70-80 DEG C, dropwise drip remaining mix monomer A again, equivalent constant duration adds initiator solution in four batches simultaneously, guarantee that mix monomer A dropwises in 2h, final obtained St/BA core emulsion,
Step 4, St/BA core emulsion temperature of reaction obtained for step 3 is maintained 80-85 DEG C, in core emulsion, shell monomer is dripped with the drop rate of 0.4ml/min ~ 1.0ml/min, equivalent constant duration adds remaining initiator solution in six batches simultaneously, after shell monomer dropwises, drip functional monomer, after standby function monomer dropping is complete to drip the identical drop rate of shell monomer at once, be warming up to 85-95 DEG C, insulation 30-60min, is cooled to room temperature, filters discharging; Namely polystyrene/butyl acrylate base compound core-shell emulsion is obtained;
In step 3, when starting to drip mix monomer A, first time adds initiator solution, adds once afterwards every half an hour, and total add-on of initiator solution is 30% ~ 40% of step 2 configuration initiator solution total mass;
In step 4, when starting to drip shell monomer, first time adds initiator solution, adds once afterwards every half an hour.
2. the preparation method of a kind of polystyrene according to claim 1/butyl acrylate base compound core-shell emulsion, it is characterized in that compound emulsifying agent described in step one be emulsifier op-10 and sodium laurylsulfonate SDS by (1 ~ 2): mixing of the mass ratio of (1 ~ 3).
3. the preparation method of a kind of polystyrene according to claim 1/butyl acrylate base compound core-shell emulsion, is characterized in that functional monomer described in step one is carboxylic olefin monomer.
4. the preparation method of a kind of polystyrene according to claim 3/butyl acrylate base compound core-shell emulsion, is characterized in that functional monomer is acrylic or methacrylic acid.
5. the preparation method of a kind of polystyrene according to claim 1/butyl acrylate base compound core-shell emulsion, is characterized in that
Be benchmark by reaction total monomer amount in step one, the mass percentage proportioning of raw material is as follows:
Deionized water: 140%
Butyl acrylate: 38%
Vinylbenzene: 30%
Methyl methacrylate: 5% ~ 29%
Functional monomer: 2.5%
Compound emulsifying agent: 4%
Ammonium persulphate: 0.45%
NaHCO
3：0.5％。
6. the preparation method of a kind of polystyrene according to claim 5/butyl acrylate base compound core-shell emulsion, to it is characterized in that in step one by reaction total monomer amount being benchmark, methyl methacrylate is 19%.
7. the preparation method of a kind of polystyrene according to claim 5/butyl acrylate base compound core-shell emulsion, to it is characterized in that in step one by reaction total monomer amount being benchmark, methyl methacrylate is 29%.
8. the preparation method of polystyrene/butyl acrylate base compound core-shell emulsion high rigidity latex film, it is characterized in that the preparation method of polystyrene/butyl acrylate base compound core-shell emulsion high rigidity latex film is undertaken by following operation: get polystyrene/butyl acrylate base compound core-shell emulsion prepared by claim 1 method, then ionic complexing agent is added, stir, bottom tiling spill glassware, at room temperature dry 24 ~ 48h, namely obtains high rigidity latex film.
9. the preparation method of a kind of polystyrene according to claim 8/butyl acrylate base compound core-shell emulsion high rigidity latex film, is characterized in that the mol ratio of the function monomer in ionic complexing agent and polystyrene/butyl acrylate base compound nucleocapsid emulsion materials is for (0 ~ 0.5): 1.
10. the preparation method of a kind of polystyrene according to claim 8/butyl acrylate base compound core-shell emulsion high rigidity latex film, is characterized in that described ionic complexing agent is ZnCl
2the aqueous solution, the hexanediamine aqueous solution and CaCl
2the aqueous solution; Wherein ZnCl
2the mass percent concentration of the aqueous solution is 0.15%-0.45%, CaCl
2the mass percent concentration of the aqueous solution is 0.20%-0.46%, and the mass percent concentration of the hexanediamine aqueous solution is 0.14%-0.40%.
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| CN108276536A (en) * | 2018-02-01 | 2018-07-13 | 东北林业大学 | A kind of GMA graft modifications polyvinyl acetate ester group inverse kernel shell lotion and preparation method thereof |
| CN109942756A (en) * | 2018-05-17 | 2019-06-28 | 北京化工大学 | One kind having gradient damping structure styrene-acrylic emulsion and can toast heavy sizing aqueous damping paint and preparation |
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| CN108192430A (en) * | 2018-02-01 | 2018-06-22 | 东北林业大学 | Styrene-acrylate core/shell type waterborne radiation curable coating and preparation method thereof and its it is light-cured into film method |
| CN108276536A (en) * | 2018-02-01 | 2018-07-13 | 东北林业大学 | A kind of GMA graft modifications polyvinyl acetate ester group inverse kernel shell lotion and preparation method thereof |
| CN108276536B (en) * | 2018-02-01 | 2020-05-19 | 东北林业大学 | GMA graft modified polyvinyl acetate based reverse core-shell emulsion and preparation method thereof |
| CN109942756A (en) * | 2018-05-17 | 2019-06-28 | 北京化工大学 | One kind having gradient damping structure styrene-acrylic emulsion and can toast heavy sizing aqueous damping paint and preparation |
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