CN102358766B - Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion - Google Patents
Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion Download PDFInfo
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Abstract
The invention relates to a synthesis method of a clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion. The method comprises the steps of: (1) dispersing inorganic clay into deionized water so as to obtain a clay suspension, then adding azobis(isobutylamidine hydrochloride) for an ion exchange reaction, thus obtaining modified clay; (2) dispersing the modified clay into deionized water, and adding an emulsifier and a monomer for a polymerization reaction; (3) adding an emulsifier, an initiator and a monomer into the emulsion obtained in step (2) for a free radical polymerization reaction, then conducting cooling, adjusting the pH value and adding a cross-linking agent, thus obtaining the core-shell polyacrylate emulsion. Characterized by simplicity, low cost and environmental friendliness, the synthesis method of the invention can prepare a polyacrylate emulsion with good film forming performance. And a latex film prepared with the emulsion has a high glass-transition temperature, high hardness and excellent mechanical properties, so that the application scope of the polyacrylate emulsion is widened, especially in the fields of water-borne coatings and adhesives, etc.
Description
Technical field
The invention belongs to the modification field of acrylic ester polymer, particularly a kind of synthetic method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion.
Background technology
Have excellent light stability and weathering resistance, good water-fast, alkaline-resisting, chemical resistance and adhesiveproperties become one of important kind of coating polymer.And the polyacrylate dispersion that is used for environment amenable water-borne coatings often by esters of acrylic acid and methyl acrylic ester monomer copolymerization and, wherein hard monomer provides the hardness of filming, water tolerance and high temperature resistance after-tackiness; Soft monomer provides the deformability of emulsion film forming, but its film forming properties is poor, freeze-thaw resistance is not good, drying rate is slow, hardness of film low and easy heat sticks the shortcomings such as cold short, has greatly limited it in the application in water-borne coatings.
For above shortcoming, at present the polyacrylate dispersion modification is comprised physical method and chemical process two classes.Physical method is to pass through physical blending, the inorganic particulate that some are little or carry out blend with other polymer emulsion, make the emulsion property that obtains be optimized (Huang S L, Polymer, 2,005 46 (6): 1865-1877, Hegedus C R, Coatings technology, 1996,68 (860): 39-48).More efficiently method is chemic modified method, the chemical modification method that proposes at present is a lot, comprise inorganic-organic hybrid (Watanabe M, Polymer Science Part A:Polymer Chemistry, 2006,44:4736-4742), acrylate and other monomer copolymerizations (Sun Zhongxin, CN 1221756A, Naghash H J, Progress in Organic Coatings, 2011,70 (1): 32-38), introduce function monomer and form crosslinking structure (Daniels A, US:6402555, Tillson H Cv, US:3219610, Liu X H, Applied Polymer Science, 2007,106 (2): 1448-1455), carry out latex particle design preparation core-shell emulsion etc.
In various method of modifying, latex particle generation crosslinking reaction when utilizing organic inorganic hybridization and film forming can well be improved the performance of polyacrylic ester.In cross-linking system, it is crosslinked that polymkeric substance occurs in the reaction that utilizes ketone hydrazine crosslinking reaction namely to utilize ketone carbonyl and hydrazine and derivative thereof to be condensed into hydrazone, this method is by increasing people's research and utilization, its superiority is that it is a kind of single component emulsion, when room temperature storage, be stable, just crosslinking reaction can occur when only having in use drying and dehydrating, greatly facilitate practical application.Recently, people (the Coatings Technology and Research such as Kessel N, 2008,5:285-297) studied DAAM crosslinking reaction and DAAM consumption to the impact of acrylic ester emulsion film forming properties, more cross-linking modified performances that can improve preferably emulsion and latex film are found in research.People (the Polymers for Advanced Technologies such as Wang R M, 2010,21 (2): 128-134) add nano silicon and shell is introduced DAAM and ADH self-crosslinking system has been synthesized the soap-free core-shell acrylic ester emulsion in conjunction with emulsifier-free emulsion polymerization, core-shell emulsion polymerization and at stratum nucleare, although improved some performances of polyacrylate dispersion, but utilize soap-free emulsion but to can not get the emulsion of high solids content, limit its industrial applications.
Thereby necessitate in conjunction with the research that organic inorganic hybridization and self-crosslinking system obtain the polyacrylate dispersion of higher solids content, and about utilizing inorganic clay and introducing the self-crosslinking system and come the method for modifying of the polyacrylate dispersion of modified core shell structure to rarely have report.
Summary of the invention
Technical problem to be solved by this invention provides a kind of synthetic method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion, and the method preparation technology is simple, and the emulsion of gained has preferably film forming properties and excellent calorifics and mechanical property.
The synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion of the present invention comprises:
(1) inorganic clay is scattered in the deionized water, strong stirring 20-40min, obtain water white slurry, then add azo-bis-isobutyrate hydrochloride (AIBA), at room temperature clay and AIBA carry out ion exchange reaction 20-28h, then filter, wash and remove unnecessary AIBA, obtain modified clay AIBA-Laponite in 40 ℃ of vacuum-dryings at last; The AIBA of modified clay AIBA-Laponite surface attachment serves as initiator in the nuclear polymerization, thereby need not to add initiator in the process of synthetic kernel;
(2) above-mentioned modified clay AIBA-Laponite is dispersed under the effect of colloid dispersion agent in the deionized water again, under stirring at room, disperseed 1-5 days; Then add the used emulsifying agent of synthetic kernel, under inert atmosphere and agitation condition, be warming up to gradually 68-72 ℃, then add the used monomer of nuclear polymerization, in 68-72 ℃ of polymerization 4-8h, at 75 ℃ of slaking 1-3h; Wherein the quality of colloid dispersion agent is modified clay 10%, and the modified clay quality is the 5-25% of nuclear monomer, and the emulsifying agent quality accounts for the 1-5% of monomer mass;
(3) add required emulsifying agent, initiator and the monomer of shell polymerization in the emulsion of step (2) gained, carry out Raolical polymerizable 5-10h in 75-78 ℃, at 80 ℃ of slaking 1-3h; When then being cooled to 45 ℃, regulating pH value is 9-10, and the adding linking agent disperses rear discharging fully and get final product until linking agent.
Inorganic clay described in the step (1) is a kind of trioctahedron montmorillonite for synthetic clay Laponite (Rockwood company).
The mass ratio of the clay described in the step (1) and deionized water is 1: 100, and the mass ratio of AIBA and clay is 1: 10-1: 5.
The mass ratio of the modified clay described in the step (2) and deionized water is 1: 50-1: 100.
Colloid dispersion agent described in the step (2) is one or more in trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99.
The used emulsifying agent of synthetic kernel described in step (2) and (3) is one or more in sodium laurylsulfonate (SLS), sodium lauryl sulphate (SDS), the polyoxyethylene nonylphenol ether (OP-10).
The used monomer of nuclear polymerization described in the step (2) is one or more in vinylbenzene (St), diacetone-acryloamide(DAA) (DAAM), the butyl acrylate (BA).
The used monomer of shell polymerization described in the step (3) is one or more in methyl methacrylate (MMA), butyl acrylate (BA), Isooctyl acrylate monomer (2-EHA) and the diacetone-acryloamide(DAA) (DAAM).
Initiator described in the step (3) is AIBA, Ammonium Persulfate 98.5 (APS) or Potassium Persulphate (KPS); Linking agent is adipic dihydrazide (ADH) or carbonic acid two hydrazides.
The mass percent that initiator quality described in the step (3) accounts for monomer is 0.5-1.5%, the emulsifying agent quality is the 1-6% of monomer mass, the mass ratio of monomer and modified clay is 5: 1-16: 1, and the mass ratio of linking agent and modified clay is 1: 2-1: 6.
Adjusting pH value described in the step (3) is for using ammoniacal liquor (NH
3H
2O) regulate.
Among the present invention take with the modified clay AIBA-Laponite of the initiator A IBA initiator source as synthetic kernel, take SLS/SDS/OP-10 as compound emulsifying agent, by the method for radical polymerization and the technique preparation nuclear of semi-continuous emulsion polymerizing, then adopt the pre-emulsification half-continuous process to prepare shell and obtain stable polyacrylate dispersion.
The advantage of the selected DAAM of the present invention and ADH self-crosslinking system is that this system can at room temperature be carried out self-crosslinking under neutral or weakly acidic condition, therefore, when emulsion stores, adds a small amount of ammoniacal liquor adjusting pH value and is 9-10, can keep well the stability of emulsion.After the ammoniacal liquor volatilization, system generation crosslinking reaction forms the film with crosslinking structure.
Experiment shows, clay is stripped from into the lamella of nano-scale, is dispersed in emulsion particle surface and the emulsion (to see accompanying drawing 1); Simultaneously, the latex film by the hud typed polyacrylate dispersion preparation of clay alteration has excellent mechanical property (seeing accompanying drawing 2); Simultaneously, along with the increase of function monomer DAAM content, the second-order transition temperature of latex film also increases (seeing accompanying drawing 3) gradually; Along with the increase of the quality of the clay that adds, the hardness of latex film increases gradually.
Beneficial effect:
(1) synthetic method of the present invention is simple, and cost is lower, and is environmentally friendly, is fit to large-scale production;
(2) polyacrylate dispersion of the present invention's preparation, not only emulsion has preferably film forming properties, and have higher second-order transition temperature, higher hardness and more excellent mechanical property by the latex film of emulsion preparation, thereby widened the range of application of polyacrylate dispersion, particularly in fields such as water-borne coatings and sizing agents.
Description of drawings
Fig. 1 is the TEM photo of latex particle;
Fig. 2 is that function monomer diacetone-acryloamide(DAA) content is on the impact of latex film mechanical property;
Fig. 3 is that function monomer diacetone-acryloamide(DAA) content is on the impact of latex film thermal property.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
(1) organic-treating of clay: the 3g clay is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.35gAIBA and carry out the organic ion permutoid reaction, reaction times 24h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1g modified clay, it is dissolved in the four-hole bottle that 100ml water is housed, and adding trisodium phosphate 0.1g, after at room temperature stirring 2d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.2g and OP-10 0.1g and leading to nitrogen 1h, then be warming up to 72 ℃, dropwise add monomer mixture (St 7g and BA 3g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously the used monomer pre-emulsion of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 2.78g, BA 5.56g, 2-EHA 1.67g and DAAM 0.6g joined successively be dissolved with emulsifying agent SDS 0.2g/OP-10 0.1g and 10ml H
2In the there-necked flask of O, emulsification 1h makes) and initiator solution (AIBA 0.1g is dissolved in the 10ml water and makes), in 2-3h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.309g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
(1) organic-treating of clay: 3g clay Laponite is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.35gAIBA and carry out the organic ion permutoid reaction, reaction times 20h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1.5g modified clay AIBA-Laponite, it is dissolved in the four-hole bottle that 100ml water is housed, and adding trisodium phosphate 0.15g, after at room temperature stirring 2d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.2g and OP-10 0.1g and leading to nitrogen 1h, then be warming up to 70 ℃, dropwise add monomer mixture (St 7g and BA 3g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously all monomer mixtures of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 2.78g, BA 5.56g, 2-EHA 1.67g and DAAM 0.6g joined successively be dissolved with emulsifying agent SDS 0.2g/OP-10 0.1g and 10ml H
2Emulsification 1h makes in the there-necked flask of O) and initiator solution (AIBA 0.06g is dissolved in the 10ml water and makes), in 2-3h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.309g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
(1) organic-treating of clay: 3g clay Laponite is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.35gAIBA and carry out the organic ion permutoid reaction, reaction times 24h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, the filter cake oven dry with obtaining gets modified clay.
(2) polymerization of nuclear: weighing 2g modified clay AIBA-Laponite, it is dissolved in the four-hole bottle that 100ml water is housed, and adding trisodium phosphate 0.2g, after at room temperature stirring 1d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.2g and OP-10 0.1g and leading to nitrogen 1h, then be warming up to 70 ℃, dropwise add monomer mixture (St 7g and BA 3g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously all monomer mixtures of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 2.78g, BA 5.56g, 2-EHA 1.67g and DAAM 0.6g joined successively be dissolved with emulsifying agent SDS 0.2g/OP-10 0.1g and 10ml H
2Emulsification 1h makes in the there-necked flask of O) and initiator solution (AIBA 0.02g is dissolved in the 10ml water and makes), in 1-2h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.309g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
(1) organic-treating of clay: the 3g clay is dissolved in the 400ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.35gAIBA and carry out the organic ion permutoid reaction, reaction times 26h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1g modified clay, it is dissolved in the four-hole bottle that 100ml water is housed, and adding trisodium phosphate 0.1g, after at room temperature stirring 2d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.2g and OP-10 0.1g and leading to nitrogen 1h, then be warming up to 68 ℃, dropwise add monomer mixture (St 7g and BA 3g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously all monomer mixtures of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 4.17g, BA 8.34g, 2-EHA 2.51g and DAAM 0.9g joined successively be dissolved with emulsifying agent SDS 0.3g/OP-10 0.15g and 10ml H
2Emulsification 1h makes in the there-necked flask of O) and initiator solution (AIBA 0.1g is dissolved in the 10ml water and makes), in 2-3h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.46g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
(1) organic-treating of clay: the 3g clay is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.35gAIBA and carry out the organic ion permutoid reaction, reaction times 28h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1.5g modified clay, it is dissolved in the four-hole bottle that 100ml water is housed, and adding trisodium phosphate 0.15g, after at room temperature stirring 5d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.3g and OP-10 0.15g and leading to nitrogen 1h, then be warming up to 70 ℃, dropwise add monomer mixture (St 10.5g and BA 4.5g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously all monomer mixtures of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 2.78g, BA 5.56g, 2-EHA 1.67g and DAAM 0.6g joined successively be dissolved with emulsifying agent SDS 0.2g/OP-10 0.1g and 10ml H
2Emulsification 1h makes in the there-necked flask of O) and initiator solution (AIBA 0.1g is dissolved in the 10ml water and makes), in 2-3h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.309g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
(1) organic-treating of clay: 3g clay Laponite is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.6gAIBA and carry out the organic ion permutoid reaction, reaction times 24h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1.5g modified clay AIBA-Laponite, it is dissolved in the four-hole bottle that 100ml water is housed, and adding tripoly phosphate sodium STPP 0.15g, after at room temperature stirring 3d, remove dissolved oxygen to wherein adding emulsifying agent SLS 0.1g and OP-10 0.15g and leading to nitrogen 1h, then be warming up to 70 ℃, dropwise add monomer mixture (St 10.5g and BA 4.5g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: drip simultaneously all monomer mixtures of shell polymerization in the above-mentioned emulsion with two constant pressure funnels and (MMA 4.17g, BA 8.34g, 2-EHA 2.51g and DAAM 0.9g joined successively be dissolved with emulsifying agent SDS 0.3g/OP-10 0.15g and 10ml H
2Emulsification 1h makes in the there-necked flask of O) and initiator solution (AIBA 0.15g is dissolved in the 10ml water and makes), in 2-3h, adding, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.46g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
Embodiment 7
(1) organic-treating of clay: 3g clay Laponite is dissolved in the 300ml deionized water by strong stirring, obtain the water white aqueous solution, then add 0.45gAIBA and carry out the organic ion permutoid reaction, reaction times 24h, with the suspension filtered that obtains, and remove unreacted AIBA with a large amount of deionized water wash, and the filter cake that obtains is dried at 40 ℃ of vacuum drying ovens, get modified clay.
(2) polymerization of nuclear: weighing 1g modified clay AIBA-Laponite, it is dissolved in the four-hole bottle that 100ml water is housed, and adding Sodium hexametaphosphate 99 0.1g, after at room temperature stirring 2d, remove dissolved oxygen to wherein adding emulsifying agent SDS 0.4g and OP-10 0.2g and leading to nitrogen 1h, then be warming up to 70 ℃, dropwise add monomer mixture (St 7g and BA 3g) in the reactor with constant pressure funnel, behind the sustained reaction 4h, be warming up to 75 ℃ of slaking 2h.
(3) polymerization of shell: in above-mentioned emulsion, drip all monomer mixture (the MMA 2.78g of shell polymerization simultaneously with two constant pressure funnels, BA 5.56g, 2-EHA 1.67g, DAAM 0.6g) with initiator solution (AIBA 0.1g is dissolved in the 10ml water), in 2-3h, add, sustained reaction 4h is warming up to 80 ℃ of slaking 2h, when polymerization finishes to be cooled to 45 ℃, drips ammoniacal liquor (NH
3H
2O) regulate PH to 9-10, add the linking agent ADH 0.309g of metering, disperse rear discharging to obtain clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion fully until linking agent.Emulsion property and film performance see Table 1.
The emulsion property of table 1 clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion and film performance
Claims (9)
1. the synthetic method of a clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion comprises:
(1) inorganic clay is scattered in the deionized water, stirs 20-40min, obtain slurry, then add azo-bis-isobutyrate hydrochloride AIBA, at room temperature clay and AIBA carry out ion exchange reaction 20-28h, then filter, wash, and final drying obtains modified clay;
(2) above-mentioned modified clay is dispersed in the deionized water under the effect of colloid dispersion agent, under stirring at room, disperseed 1-5 days; Then add the used emulsifying agent of synthetic kernel, under inert atmosphere and agitation condition, be warming up to 68-72 ℃, then add the used monomer of nuclear polymerization, in 68-72 ℃ of polymerization 4-8h, at 75 ℃ of slaking 1-3h; Wherein the quality of colloid dispersion agent is 10% of modified clay quality, and the modified clay quality is the 5-25% of nuclear monomer quality, and the emulsifying agent quality accounts for the 1-5% of monomer mass;
(3) add required emulsifying agent, initiator and the monomer of shell polymerization in the emulsion of step (2) gained, carry out Raolical polymerizable 5-10h in 75-78 ℃, at 80 ℃ of slaking 1-3h; Then be cooled to 45 ℃, regulating the pH value is 9-10, adds linking agent again, disperses rear discharging fully and get final product until linking agent.
2. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the inorganic clay described in the step (1) is synthetic clay Laponite, and this clay Laponite is a kind of trioctahedron montmorillonite.
3. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the mass ratio of the clay described in the step (1) and deionized water is 1:100, and the mass ratio of AIBA and clay is 1:10-1:5.
4. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the mass ratio of the modified clay described in the step (2) and deionized water is 1:50-1:100.
5. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the colloid dispersion agent described in the step (2) is one or more in trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99.
6. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the used monomer of the nuclear polymerization described in the step (2) is one or more in vinylbenzene, diacetone-acryloamide(DAA), the butyl acrylate.
7. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the used monomer of the shell polymerization described in the step (3) is one or more in methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, the diacetone-acryloamide(DAA); Initiator is AIBA, Ammonium Persulfate 98.5 APS or Potassium Persulphate KPS; Linking agent is adipic dihydrazide ADH or carbonic acid two hydrazides.
8. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the mass percent that the initiator quality described in the step (3) accounts for monomer is 0.5-1.5%, the emulsifying agent quality is the 1-6% of monomer mass, the mass ratio of monomer and modified clay is 5:1-16:1, and the mass ratio of linking agent and modified clay is 1:2-1:6.
9. the synthetic method of a kind of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion according to claim 1, it is characterized in that: the adjusting pH value described in the step (3) is for to regulate with ammoniacal liquor.
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| CN1847350A (en) * | 2005-04-15 | 2006-10-18 | 中国科学院化学研究所 | Pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material and its prepn process |
| CN101289523A (en) * | 2008-06-17 | 2008-10-22 | 中国海洋石油总公司 | Reversed phase emulsion polymerization organic-inorganic composite hydrophilic nano-microballoons, preparation and applications thereof |
| CN101524630A (en) * | 2009-04-14 | 2009-09-09 | 东华大学 | Preparation of nano composite gel with organic/inorganic hybrid microspheres as crosslinking points |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462282A (en) * | 2000-09-21 | 2003-12-17 | 罗姆和哈斯公司 | Emulsion polymerization methods involving lightly modified clay and compositions comprising same |
| CN1847350A (en) * | 2005-04-15 | 2006-10-18 | 中国科学院化学研究所 | Pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material and its prepn process |
| CN101289523A (en) * | 2008-06-17 | 2008-10-22 | 中国海洋石油总公司 | Reversed phase emulsion polymerization organic-inorganic composite hydrophilic nano-microballoons, preparation and applications thereof |
| CN101524630A (en) * | 2009-04-14 | 2009-09-09 | 东华大学 | Preparation of nano composite gel with organic/inorganic hybrid microspheres as crosslinking points |
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